PxMaxsm and XyMaxsm STATE-OF-THE-ART PARAXYLENE PRODUCTION TECHNOLOGIES FROM EXXONMOBIL CHEMICAL Scott Ramsey ExxonMobil Chemical Baytown,

Texas, U.S.A. Presented to 2001 World Petrochemical Conference Houston, Texas, U.S.A. February 26-27, 2001 Summary Significant advances in zeolite catalysis within ExxonMobil, which build upon the 25+ year tradition of continuous development and improvement, have resulted in the development of state-of-the-art technologies for Selective Toluene DisProportionation and Xylene Isomerization. These technologies, called PxMaxsm and XyMaxsm respectively, have recently been offered for licensing. In this paper, some of the details of these new technologies and their advantages over existing technologies will be discussed. Introduction Industry analysts suggest that the paraxylene market is not expected to tighten up for 1-2 more years. While this might be the time to conduct studies and do planning for future expansions, it is difficult to justify grass roots expenditures in the current environment with paraxylene prices so depressed. Instead, paraxylene producers are looking at alternatives that could lower the production cost of paraxylene and help them ride out this low spot in the paraxylene cycle, while preparing themselves for the next up-cycle. Since the merger of Exxon Corporation and Mobil Oil Corporation on December 1, 1999, two new technologies, PxMaxsm for Selective Toluene Disproportionation, and XyMaxsm for Xylene Isomerization have been introduced for licensing. Both of these technologies offer paraxylene producers a quick, effective option for lowering their paraxylene production cost by reducing feedstock requirements and operating costs. Furthermore, the technologies operating flexibility can enable future paraxylene production increases without hardware modifications when market conditions improve. ExxonMobil Chemicals Paraxylene Technology Suite ExxonMobils complete suite of paraxylene technologies (Figure 1), include the paraxylene selective technology now known as PxMax shown in the lower left corner, and our technologies which produce equilibrium xylenes in the upper right half of the chart. These include XyMax for xylene isomerization, TransPlus for toluene and C9+ aromatics transalkylation and MTDP-3 for conventional toluene disproportionation. PxMax and XyMax are the focus of this paper, beginning with PxMax.

Figure 1
Xylene Isomerization (XyMaxsm) CH3
Mixed Xylenes Transalkylation (TransPlusSM) CH3 + CH3 C9+ Aromatics CH3 R

Equilibrium Xylenes Processes

CH3

Para-Selective Xylenes
p-Xylene

Toluene CH3

Toluene Disproportionation (MTDP-3) CH3 2 Toluene

Selective Toluene Disproportionation (PxMaxsm)

CH3 2 Toluene

CH3

25+ Year Tradition of Continuous Development and Improvement ExxonMobils participation in technology for the paraxylene market dates back to the early 1970s with the discovery of ZSM-5 (Figure 2), and the development of shape selective zeolite catalysis. Since then ExxonMobil has introduced three generations of conventional toluene disproportionation catalyst, which produce equilibrium xylenes plus co-product benzene. With an equilibrium paraxylene concentration of only 24% in the xylene product, further processing is required to recover and increase the yield of paraxylene. This involves removing the para-isomer via selective adsorption or crystallization, followed by processing the ortho- and meta- isomers over an isomerization catalyst to convert these isomers to paraxylene by reequilibrating the mixture. This results in a large recycle loop to completely convert the other isomers into the desired paraxylene.

Figure 2
TDP Catalyst Technology Advancement Paraxylene Selective Technologies In-situ Coke Selectivation

MTDP-1 MTDP-2
1975 1984

DP ST M
19 DP 96 -3

00 -22 EM 98
19
1996

PxMaxsm
Ex-situ Permanent Selectivation

MT

19

91

MTP X

Equilibrium Xylene Technologies

19 97

Tr an sP lus

In the 1980s Mobil Oil Corporation discovered, scaled-up, and commercially demonstrated the Mobil Selective Toluene DisProportionation (MSTDP)

process, which used a novel in-situ pretreatment procedure, that for the first time made it possible to beat equilibrium, achieving over 80% paraxylene in the xylenes product. In 1991, Exxon Chemical started-up the first large-scale paraxylene selective MSTDP unit in Baytown, Texas. There are 9 total worldwide licensees of the MSTDP process to date. Continuing on the path of in-situ selectivation, but with dramatically improved performance, in 1998, the EM-2200 catalyst technology was commercialized in that same Baytown, Texas unit. At the same time EM-2200 was under development, a parallel R&D program was underway to find a way to prepare a catalyst that would not require the high temperature on-line selectivation that MSTDP required, thus greatly increasing the potential for low cost applications of the technology. The result was the ex-situ selectivated MTPX technology commercialized in 1996 by Mobil Oil at Chalmette Refinings, Louisiana refinery and subsequently applied in 1997 at Mobil Chemicals grass-roots unit in Beaumont, Texas. It is these 2 catalyst technologies, MTPX and EM-2200 that are currently being offered for licensing as part of the PxMaxsm process.

Toluene Disproportionation Technologies The simplified process flow scheme below (Figure 3) shows the usual toluene disproportionation flow with a reactor section, fractionation to separate the aromatics products, and a paraxylene recovery unit, either crystallization or absorptive separation. The key difference between the toluene disproportionation technologies offered by ExxonMobil is shown in the upper right corner. MTDP-3 yields a xylene stream to paraxylene recovery of 24% paraxylene (as limited by equilibrium), the MSTDP technology commercialized in 1991 gave 80+% paraxylene in the xylenes, whereas the PxMax technologies produce a paraxylene enriched xylenes stream containing >90% paraxylene.

Figure 3
Simplified Flow Scheme 2 +
Mixed Xylenes % PX in Xylenes MTDP-3 24 80+ MSTDP PxMax (MTPX/EM-2200) 90+

Paraxylene Toluene Feed Reactor Section Fractionation Paraxylene Recovery Mixed Xylenes

Benzene

C9+ Aromatics

Zeolite Catalyst

This increasing selectivity to paraxylene can have a significant impact on the downstream paraxylene recovery, which can be much more efficient because

of the higher concentration of paraxylene, resulting in lower costs for separation and recycle. Alternatively, the reduced recycle in the xylene production loop offers the potential to significantly increase paraxylene capacity with minimal capital investment.

Model for Para Selectivity in Zeolite The key to the greatly enhanced paraxylene selectivity relative to conventional disproportionation technology is a proprietary modification of the zeolite combined with a novel pre-treatment which selectivates the catalyst. In this model (Figure 4), the pore openings into the zeolite crystal are represented by the boxes, and the dark areas on the external surface of the zeolite represent the selectivating agent. In the case of MSTDP, and the new PxMaxsm catalyst called EM-2200, this is coke from the on-line selectivation procedure. With MTPX this is a proprietary pretreatment applied during catalyst manufacture, which is permanent.

Figure 4
Zeolite external surface Selectivating agent

Toluene

OX

MX Benzene PX

Pore opening

Paraxylene Rich Product

Smaller PX isomer diffuses 100+ times faster than MX or OX isomers

The effect of these modifications is to increase the relative diffusivity of paraxylene by several orders of magnitude compared to the larger ortho- and meta- isomers. When toluene enters the zeolite, it disproportionates to benzene and an equilibrium mix of the three xylene isomers. Because of the greater diffusivity, paraxylene exits the pores more rapidly and the remaining ortho- and meta- isomers re-equilibrate to form more paraxylene. The selectivation procedure also deactivates sites on the exterior surface of the catalyst particle where re-isomerization of the paraxylene could occur.

PxMax Superior to MSTDP Figure 5 illustrates the impact of the improvements in zeolite catalyst technology associated with the PxMax technologies, as compared to conventional STDP technologies, such as MSTDP.
To date, ExxonMobil has over 10 years of commercial experience with the MTPX and EM-2200 catalyst systems. Due to the increased activity of the PxMax catalysts, EM-2200 and MTPX, they have start-of-cycle temperatures

of 20 and 55 C, respectively lower than MSTDP, which can save utilities and suppress the formation of light gases, resulting in higher paraxylene yields. The selectivity is increased to 90+% relative to the 80+% achievable with MSTDP, which can give even lower paraxylene recovery costs. And most importantly, the paraxylene yield, as a wt% on toluene converted is increased by an absolute 5+ wt% relative to MSTDP.

Figure 5
10+ years of commercially demonstrated superior performance PxMaxsm MSTDP EM-2200 / MTPX SOC Activity, C Base -20 / -55 PX Select., wt% 80+ 90+ PX Yld, wt% Base >+5 Ex-situ selectivation (MTPX) vs In-situ coke selectivation Lower capital cost Increased retrofit potential Permanent selectivation Lower cost paraxylene recovery

The ex-situ selectivated MTPX catalyst, as compared to the in-situ or coke selectivated EM-2200 catalyst (or coke selectivated competitor technologies) has some unique advantages. First, since no high temperature on-line selectivation is required, lower temperature metallurgy can be used, resulting in lower capital costs on grass roots units, or the ability to retrofit the technology into a broader range of conventional hydroprocessing units which may be spare or idle. Second, and most importantly, the selectivation is permanent. No on-line selectivation is required either following the initial catalyst fill or after regeneration. Lastly, at 90+% paraxylene selectivity, which is only achievable on a longterm sustainable basis with our PxMax technology, the much less expensive two-stage crystallization technologies for paraxylene recovery becomes an option, further reducing costs.

Commercial Experience There are eight MSTDP units, which have over 43 years of cumulative operating experience. Our 10+ years of commercial PxMax experience (Figure 6) with both the MTPX and EM-2200 catalysts have shown them to be extremely stable and robust. All three units are still on their first cycle, with no foreseeable need for regeneration for several years. This is a dramatic improvement over the conventional STDP technologies, such as MSTDP, where the typical cycle length is less than 2 years.

Figure 6
10+ years commercial PxMaxsm operating experience Catalyst MTPX MTPX EM-2200 Location Chalmette Beaumont Baytown Unit Type Retrofit Grass Roots Retrofit Start-up 1996 1997 1998

PxMax vs. Conventional STDP Key benefits of the PxMaxsm technology include enhanced yield performance, broad operating flexibility, and debottleneck potential (Figure 7). The high 90+% selectivity to paraxylene and 5+ absolute wt% increase in paraxylene yield from the same feedstock results in a superior xylenes to benzene ratio. The lower operating temperatures and improved selectivity to paraxylene significantly reduce undesirable by-products, such as light gases. Each of these has the direct impact of reducing the cost to manufacture paraxylene.

Figure 7
Key Benefits

Enhanced yield performance

Higher paraxylene selectivity / yield Superior xylenes / benzene ratio Improved by-product distribution

Operating flexibility / debottleneck potential

Lower H2/Hydrocarbon mole ratio Lower start-of-cycle temperatures Higher selectivity Long operating cycles

PxMax also provides significant operating flexibility and debottleneck potential. Both catalyst systems operate at H2/Hydrocarbon molar ratio significantly below the 1.5-2.5 typical with other STDP technologies. This translates into utility savings or the potential to debottleneck by replacing hydrogen recycle with toluene feedstock to make more paraxylene. Lower start-of-cycle temperatures contribute to the improved selectivity, but also provide utility costs savings and longer cycle lengths. The higher selectivity (90%+) allows significant debottleneck opportunities in the paraxylene recovery equipment, which can operate much more efficiently on the highly

paraxylene enriched xylene stream. All 3 of the commercial PxMax units expect cycle lengths well in excess of 5 years. There will be no more cycles of 2 years or less, as is typical of the current STDP technologies.

Factors in the Decision to Employ PxMax In summary, the key factors in the decision to employ ExxonMobils PxMaxsm technology include (Figure 8): PxMax is commercially proven with demonstrated long-term, superior and stable performance. PxMax provides operating flexibility. A producer can process less feed and make the same paraxylene at reduced cost. Or when the market demands it, can process more fresh feed to increase paraxylene production.
PxMax provides lower benzene co-product production during normal operations, but the ability to increase severity to make more high purity benzene (>99.95%) when the market place needs it, without any significant effect on catalyst aging.

Figure 8
Commercially proven STDP technology Operating flexibility
Less fresh feed to produce same PX Process more fresh feed to increase PX production

Lower benzene co-product production High purity benzene co-product Lower utilities cost Longer operating cycles

Lower Cost Paraxylene Production

PxMax lowers utilities costs as a result of the lower start-of-cycle temperatures, lower H2/Hydrocarbon requirement, and increased purity of the paraxylene rich xylene product. Finally, it has very long operating cycles, minimizing downtime and ensuring maximum paraxylene production capability, which is important during those brief market peaks such as in 1995-96. The next peak is expected again by industry analysts in the next few years, so now is the time to be looking at application of the PxMaxsm technology. All of these attributes provide overall lower cost paraxylene production to a licensee of our PxMaxsm technologies.

PxMax Catalyst Technology Development ExxonMobil continues to be committed to the improvement and development of its toluene disproportionation and transalkylation technologies (Figure 9). We are actively working on the next generation STDP technology which will combine the extensive zeolite catalysis knowledge brought by both Exxon and Mobil to the combined ExxonMobil Corporation.

Figure 9
Next Generation Technology Under Development Paraxylene Selective Technologies

MTDP-1 MTDP-2
1975 1984

DP ST
91

00 -2 2 M
9 19 8

PxMaxsm

19

19 DP 96 -3

MT

1996

MTP

Equilibrium Xylene Technologies

19 97

Tr an

sP

lus

_____________________________________________________________

XyMaxsm ExxonMobil Chemicals Latest Advances in Xylene Isomerization From 2001 forward, ExxonMobil will be using XyMaxsm as the name for all of our dual-bed Xylene Isomerization technologies (Figure 10). Recent advances in ExxonMobils zeolite catalysis research have led to significant improvements in our xylene isomerization technology, culminating in the introduction on February 26, 2001 of our latest generation xylene isomerization catalyst, called EM-4500. EM-4500 represents the most dramatic improvement in xylenes isomerization catalyst technology from ExxonMobil in the last 10 years.

Figure 10
Xylene Isomerization Catalyst Technology Advancement

XyMaxsm
Advanced Mobil High Activity Isom.

I HA M
99 19

Higher pX feeds (e.g. from crystallizers)

MVPI MLPI MHTI MHAI

1975 1978 1981 1990

EM - 45 2
00 0

00

Mobil Vapor Phase Isom.

Mobil Low Pressure Isom.

Mobil High Temperature Isom.

Mobil High Activity Isom.

Lower pX feeds (e.g. from adsorption)

In 1975, Mobil introduced, MVPI, the Mobil Vapor Phase xylene isomerization process, the first high activity, zeolite based xylene isomerization catalyst. In 1978, Mobil introduced MLPI, the Mobil Low Pressure Isomerization process, which was capable of operating without H2 recirculation while achieving longer

cycles and lower xylene losses. In 1981, MHTI, the Mobil High Temperature Isomerization process, was introduced, and revolutionized the market. MHTI was capable of operating at higher EB conversions with even lower xylene losses. As a result, many licensee and competitor units converted to this technology to further expand throughput and paraxylene production capability. MHTI, and the technologies following it, all convert the ethylbenzene in the feed by the dealkylation reaction to produce benzene and ethane. In 1990, Mobil introduced MHAI, the Mobil High Activity Isomerization process. This technology, which utilized a high activity zeolite catalyst, pushed the envelope even further by enabling operations at even higher EB conversions with lower temperatures and lower xylenes losses. MHAI operates at EB conversions in the range of 60-75%, high weight hourly space velocity and low H2/Hydrocarbon mole ratios. These features allowed producers to further debottleneck units with no or minimal hardware modifications. In 1999, Mobil introduced Advanced MHAI, which built on our 25+ years of experience in zeolite catalysis and xylenes isomerization, pushing EB conversion even higher, with still lower xylene losses. Advanced MHAI has been getting an extremely favorable market reception. The primary subject of the xylene isomerization portion of this paper, is our new EM-4500 catalyst, which represents the most dramatic improvement in xylene isomerization technology from ExxonMobil in the last 10 years. The EM-4500 catalyst was specifically formulated to take advantage of low paraxylene content feedstocks, such as found at sites containing an adsorptive type paraxylene recovery unit, to dramatically reduce the xylene losses at high EB conversions. Each new generation of ExxonMobil xylene isomerization catalysts have features which have allowed producers to further expand their xylene isomerization units with no or minimal hardware modifications. As a result, many of the companies currently operating with MHAI or Advanced MHAI have been using ExxonMobils xylenes isomerization technology since the 1970s or early 1980s.

Commercial Experience ExxonMobil xylene isomerization technologies have a presence worldwide. There are currently 18 units, spread across all regions that are employing ExxonMobils xylene isomerization catalyst technology. These units represent approximately 30% of the worlds paraxylene production capacity via xylene isomerization. ExxonMobils Jurong refinery in Singapore is using our newest generation EM-4500 technology. Ethylbenzene Why Remove it? EB is a significant undesirable component in the C8 fraction from reformate (Figure 11). Thus, high ethylbenzene conversion is critical to the efficient

operation of the xylene isomerization loop. Consequently each successive generation of ExxonMobil xylene isomerization technology has pushed EB conversion to a new high. This is important, because, if not converted, EB builds up in the recycle loop, and it is difficult to separate from paraxylene. Its presence derates paraxylene recovery units, so higher conversion provides

Figure 11
EB present in C8 fraction from reformate High EB Conversion (EBC) important:
Builds-up in the recycle loop Difficult to separate from paraxylene Derates paraxylene recovery units

ExxonMobils dual-bed technologies based on dealkylation

Dealkylation
H2 + C2H6

EB isomerization conversion limited by equilibrium

- H2

Isomerization

+ H2

the opportunity to debottleneck the adsorptive separation or crystallization unit. ExxonMobils dual bed xylene isomerization technologies (Conventional MHAI, Advanced MHAI, and EM-4500) are all EB dealkylation based, and thus not limited by equilibrium constraints. By contrast the EB isomerization type technologies are equilibrium limited, thus ensuring a large EB recycle stream, resulting in higher costs. When our XyMax EB dealkylation based technologies have been retrofitted into EB isomerization type units we have seen 40+% debottlenecks in paraxylene production capacity. The primary modification usually being the addition of a benzene fractionation tower.

XyMax Conventional MHAI / Advanced MHAI / EM-4500 One key feature that sets the XyMaxsm technology apart from other xylenes isomerization technologies is the use of a unique dual-bed catalyst system (Figure 12).

Figure 12
Dual Bed Catalyst System
Make-up Hydrogen Compressor Hydrogen Recycle Gas Reactor Separator Paraxylene Benzene & Toluene EB and Non-As Conversion Xylene Isomerization Stabilizer Steam CW

p-X Recovery Unit C8A Heart-Cut Xylene Column C9+ Aromatics

Furnace

Isomerate

Utilizing ExxonMobils expertise in shape selective catalysis, the dual catalysts are tailored to optimize ethylbenzene dealkylation and cracking of non-aromatics in the top bed and achieve isomerization of the para-, and sometimes ortho- depleted mixed xylenes in the bottom bed. This bottom bed promotes the isomerization while minimizing disproportionation and transalkylation reactions that destroy xylenes. While the two-catalyst system is unique, the catalyst can be loaded into any down-flow reactor as the two beds are only separated by a screen. The XyMaxsm technologies are drop-in replacements for any EB dealkylation based xylenes isomerization catalyst, and can also be retrofitted into xylenes isomerization units using EB isomerization type catalysts. As first mentioned in the text associated with Figure 10, Advanced MHAI was introduced in 1999 as the replacement for Conventional MHAI in all situations. However, within ExxonMobil we realized that a further dramatic reduction in xylenes losses could be achieved with feedstocks containing low levels of paraxylene. This work resulted in the commercialization of EM-4500 in April 2000. Since Advanced MHAI and EM-4500 are enhancements over MHAI that build on the attributes of this very durable and robust catalyst, a brief discussion on MHAI technology is helpful in understanding the similarities and differences between the 3 catalyst technologies.

Conventional MHAI The key features of Conventional MHAI technology (Figure 13) are manifold, but most importantly, high EB conversion in the range of 60 to 75%, which at the time of its introduction in 1990 was pushing the limits of commercial capabilities. Of the units that are still operating, the majority operate above 70% EB conversion, with several operating at 75% EB conversion. In retrofit applications, this ability to operate at high EB conversion translates to higher fresh feed processing capability due to the reduction in recycle loop traffic. In addition, it can potentially debottleneck and increase the efficiency of the paraxylene recovery unit by increasing the concentration of paraxylene in the C8 stream. Due to the nature of the shape selectivity of the ZSM-5 based catalyst system, paraxylene approach to equilibrium is typically above 100%.

Figure 13
Technology Features

High EB Conversion
Low xylenes losses PXAE >100%

High Weight Hourly Space Velocity Low H2/Hydrocarbon mole ratio High non-aromatics conversion Long operating cycles

The Conventional MHAI catalyst operates at a weight hourly space velocity of approximately 10, significantly higher than that of most competitor processes when introduced in 1990. This translated to lower catalyst volumes for those units converting to MHAI technology or, alternatively, increased feed processing capability. In grass roots designs, it resulted in the use of a smaller reactor, lowering the capital investment. MHAI typically operates at H2/hydrocarbon molar ratios of 1.5-2.0, much lower than that of typical competitor processes. The ability of MHAI to operate effectively at low H2/Hydrocarbon mole ratio enabled retrofit applications to realize energy savings, as well as, a higher fresh feed processing capability by substituting liquid feed for recycle gas. For grass roots applications, the paraxylene producer realized capital savings associated with the use of a smaller gas compressor and savings in operating costs as a result of the lower utility requirements. In addition to these more favorable operating conditions, MHAI converts the non-aromatics in the feed. Hence, MHAI has typically been able to process unextracted feeds allowing operators to free up extraction capacity to process other feeds. Finally, the MHAI catalyst is extremely stable. As a result, operating cycles are very long, even at the highest EB conversion levels. All of the MHAI units have experienced first cycles of over four years, with one that operated for ten years without regeneration. The Advanced MHAI and EM-4500 catalysts that ExxonMobil is currently offering for license are expected to be as stable as the Conventional MHAI catalyst. Since the start-of-cycle temperature for Advanced MHAI is significantly lower than Conventional MHAI, the expected cycle lengths are expected to be at least equivalent to Conventional MHAI. All three XyMax catalysts are regenerable, if necessary.

Advanced vs. Conventional MHAI - Benefits First lets focus on the benefits of Advanced MHAI vs. Conventional MHAI (Figure 14). The Advanced MHAI catalyst technology was first operated commercially in 1999. In addition to retaining all of the advantages of Conventional MHAI, it offers superior yield performance, broader operating

Figure 14
Benefits

Enhanced yield performance

Higher paraxylene yield Improved by-product distribution

Operating flexibility / debottleneck potential

Higher EB Conversion Higher Space Velocity Lower H2/HC mole ratio Lower Start-Of-Cycle temperature Customized for low/high EBC

Cycle length similar to conventional MHAI

flexibility and increased debottleneck potential. The enhanced yield performance is manifested in the approximately 20% reduction in xylenes losses, compared to Conventional MHAI, when operated at the same EB conversion. The lower xylenes losses associated with Advanced MHAI are a result of the higher selectivity of the catalyst for EB dealkylation. In addition, undesirable reactions such as disproportionation of xylenes to produce toluene and C9 aromatics and reverse toluene disproportionation to produce toluene are suppressed. The net result is a reduction in by-product toluene and heavies. The Advanced MHAI catalyst has a highly optimized ethylene saturation component. As a result, Advanced MHAI technology produces a benzene product with purity in excess of that specified for nitration grade, even at conditions known to promote aromatics saturation. Another benefit is even higher non-aromatics conversion than Conventional MHAI. The broader operating flexibility includes a much wider range of EB conversion, higher space velocity, lower H2/Hydrocarbon mole ratio, and lower temperature requirements. Advanced MHAI can operate at a significantly wider range of EB conversions than Conventional MHAI. The catalyst system can be optimized to operate at EB conversions as low as 35%. The low EB conversion could potentially benefit paraxylene producers using xylene isomerization catalysts that isomerize the EB to xylenes. This type of process operates at low EB conversion, in the range of 35%, and typically with a high H2/Hydrocarbon mole ratio in the range of 4 to 5. While Advanced MHAI converts the EB to benzene and not mixed xylenes, the xylene losses at low ethylbenzene conversion levels are very low. Moreover, Advanced MHAI operates at much lower H2/Hydrocarbon mole ratio. Thus, in applications where the level of EB in the feed is relatively low, use of Advanced MHAI catalyst can result in a nearly equivalent paraxylene production, but at a lower cost. At the other end of the spectrum, Advanced MHAI has the capability to operate at higher ethylbenzene conversion levels than Conventional MHAI, while maintaining low xylenes losses. This gives the paraxylene producer the ability to further debottleneck existing EB dealkylation type units without hardware modifications. It may also expand the capacity of the paraxylene recovery unit due to the higher concentration of paraxylene in the C8 aromatics feed. Advanced MHAI can operate at higher weight hourly space velocity than Conventional MHAI while maintaining superior yield performance. Paraxylene producers can capitalize on this higher WHSV in a variety of ways. For cases where the reactor loading limits throughput, the higher WHSV capability enables increasing the fresh feed rate. In cases where the fresh feed rate has already been maximized within the downstream processing constraints, catalyst loading can be reduced while maintaining constant paraxylene production. In this case, the fresh feed rate will also be reduced due to lower

xylenes yield loss, leading to savings in raw material costs. In grass roots applications, there are capital savings associated with the use of a smaller reactor. While Conventional MHAI typically operates at a H2/Hydrocarbon mole ratio lower than that of other xylene isomerization processes, the Advanced MHAI process operates at an even lower ratio. The lower H2/Hydrocarbon mole ratio has a major impact in both grass roots and retrofit applications. In grass roots applications, for a given mixed xylenes feed rate the size of the recycle gas compressor and associated gas handling equipment such as heaters, valves, exchangers can be reduced, leading to lower capital investment. In addition to the capital savings, utility costs can also be significantly reduced. In retrofit applications, utility costs can be reduced at constant paraxylene production. Lower H2/Hydrocarbon mole ratio also benefits retrofit applications by enabling a debottleneck of the xylenes isomerization unit in cases where the mixed xylenes feed is limited due to compressor or hydraulic constraints. The Advanced MHAI process operates at a significantly lower temperature than Conventional MHAI. The ability to operate at lower start-of-cycle temperature results in an expanded operating window which, when coupled with the low aging rate of the Advanced MHAI catalyst, leads to long operating cycles.

Advanced vs. Conventional MHAI - Yields The table below (Figure 15) shows some of the yield benefits associated with the Advanced MHAI when compared to Conventional MHAI. To simplify comparisons, EB conversion was kept constant and thus the data only show the benefits that result from the enhanced yield performance. Absolute feed and products shifts are in thousands of metric tons per year. The fresh feed composition is shown near the bottom of the table. At constant paraxylene production of 300 thousand metric tons per year, the economic benefit is shown in a lower fresh feed requirement of 6,500 metric tons a year. At

Figure 15
Feed / Temperature / Product Shift
Conv. MHAI Advanced MHAI
Shift vs. Conv. MHAI
Const. PX Const. FF.

Mixed Xylenes, kta SOC Temp, oC Products, kta Light Gas Benzene Toluene Paraxylene Heavies

Base Base Base Base Base 300 Base

(6.5) -20 (0.1) 1.5 (6.4) (1.5)

-20 0.2 2.0 (6.0) 5.1 (1.3)

Bases: 1) Fresh Feed, wt%: EB-15, PX-21, MX-43, OX-21 2) Constant EB Conversion

constant fresh feed, the paraxylene production increases by 5,100 metric tons. The more favorable by-product distribution can also be observed.

EM-4500 vs. Conventional MHAI - Benefits Next lets focus on the benefits of ExxonMobils latest xylene isomerization technology EM-4500 versus Conventional MHAI (Figure 16). The EM-4500 catalyst technology, which was commercialized in April 2000 in ExxonMobils Jurong refinery, represents a dramatic improvement over Conventional MHAI, and even Advanced MHAI at sites with adsorptive type paraxylene recovery, where the paraxylene content in the isomerization feed is low. Utilizing the latest advances in zeolite catalysis available within ExxonMobil, this technology pushes the limits on xylene isomerization. In addition to retaining many of the advantages of Advanced MHAI, it offers superior yield performance, and further increased debottleneck potential.

Figure 16
Benefits

Enhanced yield performance

>65% Reduction in xylene losses per pass Improved by-product distribution

Operating flexibility / debottleneck potential

Higher EB conversion Lower H2/HC mole ratio

Cycle length similar to MHAI / Advanced MHAI Maximum benefits for sites with low paraxylene feedstock (e.g. adsorptive type pX recovery)

The enhanced yield performance compared to Conventional MHAI is manifested in the greater than 65% reduction in per pass xylene losses at the same EB conversion and improved by-product distribution. This is a result of the unique, highly shape selective proprietary catalyst technology incorporated into the EM-4500 catalyst system. Improved operating flexibility and debottleneck potential are a result of the higher EB conversion and lower H2/Hydrocarbon molar ratio possible with this new catalyst. Operating at higher EB conversion increases the fresh feed processing capacity of the xylenes isomerization unit by reducing recycle loop traffic. It may also expand the capacity of the paraxylene recovery unit because of the higher concentration of paraxylene in the feed. Because of the ultra-stable nature of the EM-4500 catalyst technology, the H2/Hydrocarbon molar ratio can be further reduced. This can benefit retrofit applications by enabling a debottleneck in the case where mixed xylene feed is limited due to compressor or hydraulic constraints. Cycle lengths are expected to be similar in length to Conventional MHAI and the catalyst is regenerable.

EM-4500 vs. Conventional MHAI - Yields In Figure 17 the two right columns of data, representing the yields of EM-4500 have been added. Note that this example is for a site with adsorptive type paraxylene recovery. As before, to simplify the comparisons, we have kept operating conditions equivalent and are only showing the benefits that result from the enhanced yield performance. Absolute feed and products shifts are in thousands of metric tons per year. At constant paraxylene production of 300 thousand metric tons per year, the economic benefit is shown in a lower fresh feed requirement of 19,100 metric tons a year compared to Conventional MHAI. At constant fresh feed, the paraxylene production increases by 15,600 metric tons per year, from what is typically a simple dropin catalyst replacement.

Figure 17
Feed / Temperature / Product Shift
Conv. MHAI Advanced MHAI EM-4500

Absolute Shift vs. Conv. MHAI

Const. PX Const. FF. Const. PX Const. FF.

Mixed Xylenes, kta SOC Temp, oC Products, kta Light Gas Benzene Toluene Paraxylene Heavies

Base Base Base Base Base 300 Base

(6.5) -20 (0.1) 1.5 (6.4) (1.5)

-20 0.2 2.0 (6.0) 5.1 (1.3)

(19.1) Base (0.4) 1.6 (14.8) (5.5)

Base 0.4 3.5 (14.3) 15.6 (5.1)

Bases: 1) Fresh Feed, wt%: EB-15, PX-21, MX-43, OX-21 2) Constant EB Conversion 3) Adsorptive type paraxylene recovery

There are a total of 5 Advanced MHAI units operating at this time. The first commercial application of EM-4500 started-up in April 2000 at ExxonMobils Jurong Refinery in Singapore and performance has been exceeding expectations.

XyMax: Advanced MHAI & EM-4500 In summary, in retrofits applications, the recently introduced XyMaxsm catalyst technologies, known as Advanced MHAI and EM-4500 can contribute significantly to a net lower paraxylene production cost (Figure 18). This is a result of the increased operating flexibility, lower utility costs, lower catalyst requirements and long operating cycles.

Figure 18
Benefits in Retrofit Applications

Operating flexibility
Less fresh feed to produce same PX Process more fresh feed to increase PX production

Lower utilities costs Lower catalyst requirement Long operating cycles

Lower Cost Paraxylene Production

Furthermore, the technologies operating flexibility can enable future paraxylene production increases without hardware modifications when market conditions improve.

XyMax Research Continues Even with the significant improvements explained in this paper, ExxonMobil continues to be committed to the improvement and development of its xylene isomerization technology. We are already working on the next generation xylene isomerization technology (Figure 19). This commitment has allowed our licensees to steadily enhance their competitive position by taking advantage of the improvements in technology we have offered through the years.

Figure 19
ExxonMobil Technology Advances Continue XyMaxsm
AM 9 9
19

I HA

Higher pX feeds

MVPI MLPI MHTI MHAI

1975 1978 1981 1990

EM 20 450 00 0
Lower pX feeds

ParamaXsm Alliance with IFP In 1998, ExxonMobil Chemical and IFP formed an Alliance called ParamaXsm, with the objective of bringing together, under a single source licensor (IFP), the best technologies for grass roots aromatics complexes (Figure 20). The recently introduced XyMaxsm technology using the EM-4500 catalyst is being added to the ParamaX portfolio. For grass roots applications, please contact IFP and for retrofit applications please contact ExxonMobil Chemical. Additional information on ExxonMobil Chemicals Technology Sales and Licensing activities can be found on our web page at: www.exxonmobilchemicaltsl.com .
Figure 20
IFP - Single Source Technology and Service Provider for Grass Roots BTX Aromatics Complexes

IFP
Reformer AromizingTM Hydrotreating ArofiningTM Eluxyl BTX Sulfolane Extraction* Morphylane Extractive Dist.* OctafiningTM II* / Oparis Crystallization*
* via licensing rights

ExxonMobil
XyMaxsm - Advanced MHAI - EM-4500 MLPI MTDP-3 TransPlussm

Scott A. Ramsey Xylenes Licensing Manager

scott.a.ramsey@exxon.com

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