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 Chemical’s Paraxylene Technology Suite ExxonMobil’s 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.

followed by processing the ortho. This involves removing the para-isomer via selective adsorption or crystallization. This results in a large recycle loop to completely convert the other isomers into the desired paraxylene.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 ExxonMobil’s participation in technology for the paraxylene market dates back to the early 1970’s with the discovery of ZSM-5 (Figure 2). and commercially demonstrated the Mobil Selective Toluene DisProportionation (MSTDP) .and meta.isomers over an isomerization catalyst to convert these isomers to paraxylene by reequilibrating the mixture. Since then ExxonMobil has introduced three generations of conventional toluene disproportionation catalyst. With an equilibrium paraxylene concentration of only 24% in the xylene product. scaled-up. which produce equilibrium xylenes plus co-product benzene. and the development of shape selective zeolite catalysis. 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 1980’s Mobil Oil Corporation discovered. further processing is required to recover and increase the yield of paraxylene.

which used a novel in-situ pretreatment procedure. Texas. There are 9 total worldwide licensees of the MSTDP process to date. MTPX and EM-2200 that are currently being offered for licensing as part of the PxMaxsm process. in 1998. Continuing on the path of in-situ selectivation. The result was the ex-situ selectivated MTPX technology commercialized in 1996 by Mobil Oil at Chalmette Refining’s. the EM-2200 catalyst technology was commercialized in that same Baytown. 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. It is these 2 catalyst technologies. fractionation to separate the aromatics products. and a paraxylene recovery unit. Louisiana refinery and subsequently applied in 1997 at Mobil Chemical’s grass-roots unit in Beaumont. but with dramatically improved performance. which can be much more efficient because . achieving over 80% paraxylene in the xylenes product. Exxon Chemical started-up the first large-scale paraxylene selective MSTDP unit in Baytown.process. Toluene Disproportionation Technologies The simplified process flow scheme below (Figure 3) shows the usual toluene disproportionation flow with a reactor section. At the same time EM-2200 was under development. the MSTDP technology commercialized in 1991 gave 80+% paraxylene in the xylenes. The key difference between the toluene disproportionation technologies offered by ExxonMobil is shown in the upper right corner. 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. MTDP-3 yields a xylene stream to paraxylene recovery of 24% paraxylene (as limited by equilibrium). that for the first time made it possible to beat equilibrium. either crystallization or absorptive separation. In 1991. thus greatly increasing the potential for low cost applications of the technology. Texas. Texas unit. whereas the PxMax technologies produce a paraxylene enriched xylenes stream containing >90% paraxylene.

of the higher concentration of paraxylene. 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. the pore openings into the zeolite crystal are represented by the boxes. The selectivation procedure also deactivates sites on the exterior surface of the catalyst particle where re-isomerization of the paraxylene could occur. Due to the increased activity of the PxMax catalysts.isomers. In the case of MSTDP. and the new PxMaxsm catalyst called EM-2200. which is permanent. PxMax Superior to MSTDP Figure 5 illustrates the impact of the improvements in zeolite catalyst technology associated with the PxMax technologies. such as MSTDP. ExxonMobil has over 10 years of commercial experience with the MTPX and EM-2200 catalyst systems. paraxylene exits the pores more rapidly and the remaining ortho. it disproportionates to benzene and an equilibrium mix of the three xylene isomers. With MTPX this is a proprietary pretreatment applied during catalyst manufacture. the reduced recycle in the xylene production loop offers the potential to significantly increase paraxylene capacity with minimal capital investment.and meta. as compared to conventional STDP technologies.isomers re-equilibrate to form more paraxylene. and the dark areas on the external surface of the zeolite represent the selectivating agent. this is coke from the on-line selectivation procedure. Because of the greater diffusivity. resulting in lower costs for separation and recycle. EM-2200 and MTPX.and meta. Alternatively. they have start-of-cycle temperatures . In this model (Figure 4). 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. To date. When toluene enters the zeolite.

since no high temperature on-line selectivation is required. Commercial Experience There are eight MSTDP units.. the paraxylene yield. ºC Base -20 / -55 – PX Select. the much less expensive two-stage crystallization technologies for paraxylene recovery becomes an option. lower temperature metallurgy can be used. Figure 5 • 10+ years of commercially demonstrated superior performance PxMaxsm MSTDP EM-2200 / MTPX – SOC Activity. at 90+% paraxylene selectivity.of 20 and 55 °C. wt% 80+ 90+ – PX Yld. or the ability to retrofit the technology into a broader range of conventional hydroprocessing units which may be spare or idle. which is only achievable on a longterm sustainable basis with our PxMax technology. with no foreseeable need for regeneration for several years. and most importantly. All three units are still on their first cycle. respectively lower than MSTDP. the selectivation is permanent. No on-line selectivation is required either following the initial catalyst fill or after regeneration. The selectivity is increased to 90+% relative to the 80+% achievable with MSTDP. which can save utilities and suppress the formation of light gases. which can give even lower paraxylene recovery costs. further reducing costs. . where the typical cycle length is less than 2 years. 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. such as MSTDP. This is a dramatic improvement over the conventional STDP technologies. Lastly. Second. as a wt% on toluene converted is increased by an absolute 5+ wt% relative to MSTDP. which have over 43 years of cumulative operating experience. resulting in higher paraxylene yields. resulting in lower capital costs on grass roots units. 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. First. as compared to the in-situ or coke selectivated EM-2200 catalyst (or coke selectivated competitor technologies) has some unique advantages. And most importantly.

5 typical with other STDP technologies.5-2. Conventional STDP Key benefits of the PxMaxsm technology include enhanced yield performance.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. 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. Each of these has the direct impact of reducing the cost to manufacture paraxylene. which can operate much more efficiently on the highly . but also provide utility costs savings and longer cycle lengths. The lower operating temperatures and improved selectivity to paraxylene significantly reduce undesirable by-products. Both catalyst systems operate at H2/Hydrocarbon molar ratio significantly below the 1. 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. such as light gases. 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. The higher selectivity (90%+) allows significant debottleneck opportunities in the paraxylene recovery equipment. broad operating flexibility. and debottleneck potential (Figure 7).

Or when the market demands it. The next peak is expected again by industry analysts in the next few years.95%) when the market place needs it. which is important during those brief market peaks such as in 1995-96. so now is the time to be looking at application of the PxMaxsm technology. as is typical of the current STDP technologies. 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. minimizing downtime and ensuring maximum paraxylene production capability. Factors in the Decision to Employ PxMax In summary. There will be no more cycles of 2 years or less. 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. can process more fresh feed to increase paraxylene production. lower H2/Hydrocarbon requirement. superior and stable performance. . Finally. All 3 of the commercial PxMax units expect cycle lengths well in excess of 5 years.paraxylene enriched xylene stream. it has very long operating cycles. PxMax provides operating flexibility. and increased purity of the paraxylene rich xylene product. without any significant effect on catalyst aging. but the ability to increase severity to make more high purity benzene (>99. PxMax provides lower benzene co-product production during normal operations. All of these attributes provide overall lower cost paraxylene production to a licensee of our PxMaxsm technologies. A producer can process less feed and make the same paraxylene at reduced cost. PxMax Catalyst Technology Development ExxonMobil continues to be committed to the improvement and development of its toluene disproportionation and transalkylation technologies (Figure 9). the key factors in the decision to employ ExxonMobil’s PxMaxsm technology include (Figure 8): PxMax is commercially proven with demonstrated long-term.

zeolite based xylene isomerization catalyst. Mobil introduced MLPI. from adsorption) In 1975. Lower pX feeds (e. the Mobil Low Pressure Isomerization process. Figure 10 Xylene Isomerization Catalyst Technology Advancement XyMaxsm Advanced Mobil High Activity Isom. Mobil introduced. Mobil High Activity Isom.Figure 9 Next Generation Technology Under Development Paraxylene Selective Technologies MTDP-1 MTDP-2 1975 1984 M DP ST 91 E 00 -2 2 M 9 19 8 PxMaxsm 19 19 DP 96 -3 MT 1996 MTP X Equilibrium Xylene Technologies 19 97 Tr an sP lus _____________________________________________________________ XyMaxsm – ExxonMobil Chemical’s Latest Advances in Xylene Isomerization From 2001 forward. from crystallizers) MVPI MLPI MHTI MHAI 1975 1978 1981 1990 EM . culminating in the introduction on February 26.g. which was capable of operating without H2 recirculation while achieving longer . Recent advances in ExxonMobil’s zeolite catalysis research have led to significant improvements in our xylene isomerization technology.g.45 2 00 0 00 Mobil Vapor Phase Isom. 2001 of our latest generation xylene isomerization catalyst. the Mobil Vapor Phase xylene isomerization process. called EM-4500. MVPI. A I HA M 99 19 Higher pX feeds (e. ExxonMobil will be using XyMaxsm as the name for all of our dual-bed Xylene Isomerization technologies (Figure 10). Mobil Low Pressure Isom. In 1978. EM-4500 represents the most dramatic improvement in xylenes isomerization catalyst technology from ExxonMobil in the last 10 years. the first high activity. Mobil High Temperature Isom.

and the technologies following it. which built on our 25+ years of experience in zeolite catalysis and xylenes isomerization. high weight hourly space velocity and low H2/Hydrocarbon mole ratios. pushing EB conversion even higher. As a result. MHTI. to dramatically reduce the xylene losses at high EB conversions. the Mobil High Activity Isomerization process. As a result. is our new EM-4500 catalyst. with still lower xylene losses. ExxonMobil’s Jurong refinery in Singapore is using our newest generation EM-4500 technology. The primary subject of the xylene isomerization portion of this paper. These units represent approximately 30% of the world’s paraxylene production capacity via xylene isomerization. MHTI was capable of operating at higher EB conversions with even lower xylene losses. high ethylbenzene conversion is critical to the efficient . such as found at sites containing an adsorptive type paraxylene recovery unit. which utilized a high activity zeolite catalyst.cycles and lower xylene losses. MHTI. In 1990. many licensee and competitor units converted to this technology to further expand throughput and paraxylene production capability. Advanced MHAI has been getting an extremely favorable market reception. was introduced. There are currently 18 units. and revolutionized the market. all convert the ethylbenzene in the feed by the dealkylation reaction to produce benzene and ethane. MHAI operates at EB conversions in the range of 60-75%. spread across all regions that are employing ExxonMobil’s xylene isomerization catalyst technology. Mobil introduced Advanced MHAI. These features allowed producers to further debottleneck units with no or minimal hardware modifications. 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. Commercial Experience ExxonMobil xylene isomerization technologies have a presence worldwide. the Mobil High Temperature Isomerization process. many of the companies currently operating with MHAI or Advanced MHAI have been using ExxonMobil’s xylenes isomerization technology since the 1970s or early 1980s. pushed the envelope even further by enabling operations at even higher EB conversions with lower temperatures and lower xylenes losses. Ethylbenzene – Why Remove it? EB is a significant undesirable component in the C8 fraction from reformate (Figure 11). 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. In 1999. Mobil introduced MHAI. This technology. Thus. In 1981.

and thus not limited by equilibrium constraints. ExxonMobil’s dual bed xylene isomerization technologies (Conventional MHAI. thus ensuring a large EB recycle stream. When our XyMax EB dealkylation based technologies have been retrofitted into EB isomerization type units we have seen 40+% debottlenecks in paraxylene production capacity. Figure 12 Dual Bed Catalyst System Make-up Hydrogen Compressor Hydrogen Recycle Gas Reactor Separator Paraxylene Benzene & Toluene EB and Non-A’s Conversion Xylene Isomerization Stabilizer Steam CW p-X Recovery Unit C8A Heart-Cut Xylene Column C9+ Aromatics Furnace Isomerate .H2 Isomerization + + H2 the opportunity to debottleneck the adsorptive separation or crystallization unit. This is important.operation of the xylene isomerization loop. Its presence derates paraxylene recovery units. EB builds up in the recycle loop. Consequently each successive generation of ExxonMobil xylene isomerization technology has pushed EB conversion to a new high. By contrast the EB isomerization type technologies are equilibrium limited. 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). Advanced MHAI. because. if not converted. 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 • ExxonMobil’s dual-bed technologies based on dealkylation Dealkylation H2 + C2H6 • EB isomerization conversion limited by equilibrium . The primary modification usually being the addition of a benzene fractionation tower. and it is difficult to separate from paraxylene. resulting in higher costs. and EM-4500) are all EB dealkylation based.

However. and can also be retrofitted into xylenes isomerization units using EB isomerization type catalysts. but most importantly.depleted mixed xylenes in the bottom bed. Conventional MHAI The key features of Conventional MHAI technology (Figure 13) are manifold. with several operating at 75% EB conversion. the catalyst can be loaded into any down-flow reactor as the two beds are only separated by a screen. it can potentially debottleneck and increase the efficiency of the paraxylene recovery unit by increasing the concentration of paraxylene in the C8 stream. This bottom bed promotes the isomerization while minimizing disproportionation and transalkylation reactions that destroy xylenes. While the two-catalyst system is unique. the dual catalysts are tailored to optimize ethylbenzene dealkylation and cracking of non-aromatics in the top bed and achieve isomerization of the para-. a brief discussion on MHAI technology is helpful in understanding the similarities and differences between the 3 catalyst technologies. This work resulted in the commercialization of EM-4500 in April 2000. this ability to operate at high EB conversion translates to higher fresh feed processing capability due to the reduction in recycle loop traffic. Of the units that are still operating. which at the time of its introduction in 1990 was pushing the limits of commercial capabilities. the majority operate above 70% EB conversion. Advanced MHAI was introduced in 1999 as the replacement for Conventional MHAI in all situations. paraxylene approach to equilibrium is typically above 100%. Due to the nature of the shape selectivity of the ZSM-5 based catalyst system. within ExxonMobil we realized that a further dramatic reduction in xylenes losses could be achieved with feedstocks containing low levels of paraxylene. In addition. 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 . Since Advanced MHAI and EM-4500 are enhancements over MHAI that build on the attributes of this very durable and robust catalyst. high EB conversion in the range of 60 to 75%. The XyMaxsm technologies are drop-in replacements for any EB dealkylation based xylenes isomerization catalyst. As first mentioned in the text associated with Figure 10.Utilizing ExxonMobil’s expertise in shape selective catalysis. and sometimes ortho. In retrofit applications.

as well as.5-2. MHAI converts the non-aromatics in the feed. 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 grass roots designs.The Conventional MHAI catalyst operates at a weight hourly space velocity of approximately 10. lowering the capital investment. MHAI typically operates at H2/hydrocarbon molar ratio’s of 1. Conventional MHAI (Figure 14). operating cycles are very long. a higher fresh feed processing capability by substituting liquid feed for recycle gas. This translated to lower catalyst volumes for those units converting to MHAI technology or. if necessary. Since the start-of-cycle temperature for Advanced MHAI is significantly lower than Conventional MHAI. increased feed processing capability. it offers superior yield performance. 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. Conventional MHAI . Finally. Advanced vs. All three XyMax catalysts are regenerable. significantly higher than that of most competitor processes when introduced in 1990. the MHAI catalyst is extremely stable. alternatively. even at the highest EB conversion levels. the expected cycle lengths are expected to be at least equivalent to Conventional MHAI.Benefits First let’s focus on the benefits of Advanced MHAI vs. MHAI has typically been able to process unextracted feeds allowing operators to free up extraction capacity to process other feeds. As a result. All of the MHAI units have experienced first cycles of over four years. In addition to retaining all of the advantages of Conventional MHAI. much lower than that of typical competitor processes. For grass roots applications. with one that operated for ten years without regeneration. The Advanced MHAI catalyst technology was first operated commercially in 1999. it resulted in the use of a smaller reactor. Hence. The ability of MHAI to operate effectively at low H2/Hydrocarbon mole ratio enabled retrofit applications to realize energy savings.0. 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 . In addition to these more favorable operating conditions.

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

Yields The table below (Figure 15) shows some of the yield benefits associated with the Advanced MHAI when compared to Conventional MHAI. utility costs can also be significantly reduced.0 (6. 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. kta SOC Temp.3) Bases: 1) Fresh Feed.xylenes yield loss. While Conventional MHAI typically operates at a H2/Hydrocarbon mole ratio lower than that of other xylene isomerization processes. MHAI Const. In retrofit applications.0) 5. To simplify comparisons. Mixed Xylenes. In addition to the capital savings. Conventional MHAI . The lower H2/Hydrocarbon mole ratio has a major impact in both grass roots and retrofit applications. leading to lower capital investment. OX-21 2) Constant EB Conversion .4) (1. Conv. the economic benefit is shown in a lower fresh feed requirement of 6. wt%: EB-15.5) -20 (0. MHAI Advanced MHAI Shift vs.2 2.1) 1. oC Products. FF. Advanced vs. valves. for a given mixed xylenes feed rate the size of the recycle gas compressor and associated gas handling equipment such as heaters. PX-21.5) -20 0. At constant paraxylene production of 300 thousand metric tons per year. EB conversion was kept constant and thus the data only show the benefits that result from the enhanced yield performance.1 (1. kta Light Gas Benzene Toluene Paraxylene Heavies Base Base Base Base Base 300 Base (6. PX Const. there are capital savings associated with the use of a smaller reactor. The fresh feed composition is shown near the bottom of the table. MX-43. leads to long operating cycles. utility costs can be reduced at constant paraxylene production. In grass roots applications. the Advanced MHAI process operates at an even lower ratio. The ability to operate at lower start-of-cycle temperature results in an expanded operating window which. exchangers can be reduced.5 (6.500 metric tons a year. when coupled with the low aging rate of the Advanced MHAI catalyst. In grass roots applications. Absolute feed and products shifts are in thousands of metric tons per year. At Figure 15 Feed / Temperature / Product Shift Conv. leading to savings in raw material costs.

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. Utilizing the latest advances in zeolite catalysis available within ExxonMobil. it offers superior yield performance. EM-4500 vs. This can benefit retrofit applications by enabling a debottleneck in the case where mixed xylene feed is limited due to compressor or hydraulic constraints. This is a result of the unique. In addition to retaining many of the advantages of Advanced MHAI. The EM-4500 catalyst technology. Operating at higher EB conversion increases the fresh feed processing capacity of the xylenes isomerization unit by reducing recycle loop traffic. The more favorable by-product distribution can also be observed. the paraxylene production increases by 5. Cycle lengths are expected to be similar in length to Conventional MHAI and the catalyst is regenerable. represents a dramatic improvement over Conventional MHAI. . which was commercialized in April 2000 in ExxonMobil’s Jurong refinery. where the paraxylene content in the isomerization feed is low. and further increased debottleneck potential.Benefits Next let’s focus on the benefits of ExxonMobil’s latest xylene isomerization technology EM-4500 versus Conventional MHAI (Figure 16). and even Advanced MHAI at sites with adsorptive type paraxylene recovery. highly shape selective proprietary catalyst technology incorporated into the EM-4500 catalyst system. the H2/Hydrocarbon molar ratio can be further reduced. Conventional MHAI . Because of the ultra-stable nature of the EM-4500 catalyst technology.constant fresh feed. this technology pushes the limits on xylene isomerization.100 metric tons. 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.g. It may also expand the capacity of the paraxylene recovery unit because of the higher concentration of paraxylene in the feed. 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.

MHAI Advanced MHAI EM-4500 Absolute Shift vs. Conv. Figure 17 Feed / Temperature / Product Shift Conv. FF. representing the yields of EM-4500 have been added. in retrofits applications.1) 1. This is a result of the increased operating flexibility.EM-4500 vs.5 (14. Note that this example is for a site with adsorptive type paraxylene recovery.5) -20 0.4) 1. Absolute feed and products shifts are in thousands of metric tons per year.0) 5. The first commercial application of EM-4500 started-up in April 2000 at ExxonMobil’s Jurong Refinery in Singapore and performance has been exceeding expectations. Conventional MHAI . the recently introduced XyMaxsm catalyst technologies. MX-43. FF. from what is typically a simple dropin catalyst replacement. Mixed Xylenes. PX Const.8) (5.5 (6. OX-21 2) Constant EB Conversion 3) Adsorptive type paraxylene recovery There are a total of 5 Advanced MHAI units operating at this time.0 (6.1 (1. XyMax: Advanced MHAI & EM-4500 In summary. wt%: EB-15. kta SOC Temp.1) Base (0.600 metric tons per year.5) -20 (0. to simplify the comparisons. At constant paraxylene production of 300 thousand metric tons per year. .2 2. the economic benefit is shown in a lower fresh feed requirement of 19. PX-21. oC Products. known as Advanced MHAI and EM-4500 can contribute significantly to a net lower paraxylene production cost (Figure 18). PX Const. As before. lower utility costs.6 (5.3) 15.5) Base 0. the paraxylene production increases by 15.Yields In Figure 17 the two right columns of data.100 metric tons a year compared to Conventional MHAI.1) Bases: 1) Fresh Feed. At constant fresh feed.4 3.6 (14. MHAI Const.4) (1. lower catalyst requirements and long operating cycles. we have kept operating conditions equivalent and are only showing the benefits that result from the enhanced yield performance.3) (19. kta Light Gas Benzene Toluene Paraxylene Heavies Base Base Base Base Base 300 Base (6. Const.

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. XyMax – Research Continues Even with the significant improvements explained in this paper. 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 . ExxonMobil continues to be committed to the improvement and development of its xylene isomerization technology.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. We are already working on the next generation xylene isomerization technology (Figure 19). the technologies operating flexibility can enable future paraxylene production increases without hardware modifications when market conditions improve.

ParamaXsm Alliance with IFP In 1998. There is no warranty against patent infringement. please contact IFP and for retrofit applications please contact ExxonMobil Chemical. The user may forward. or processes described. and/or photocopy this copyrighted document only if unaltered and complete. or "ExxonMobil" are used for convenience. or injury directly or indirectly suffered or incurred as a result of or related to anyone using or relying on any of the information in this document. warrant.* OctafiningTM II* / Oparis Crystallization* * via licensing rights ExxonMobil • XyMaxsm . materials. and may include any one or more of ExxonMobil Chemical Company. The recently introduced XyMaxsm technology using the EM-4500 catalyst is being added to the ParamaX portfolio. fitness for a particular purpose. The information in this document relates only to the named product or materials when not in combination with any other product or materials. or otherwise guarantee.a. Exxon Mobil Corporation. expressly or impliedly. “we”. or completeness of this information or the products. the best technologies for grass roots aromatics complexes (Figure 20). under a single source licensor (IFP). Additional information on ExxonMobil Chemical’s Technology Sales and Licensing activities can be found on our web page at: www. "ExxonMobil Chemical".com ©2000 ExxonMobil. The terms. suitability.ramsey@exxon.com . reliability. The user is solely responsible for all determinations regarding any use of material or product and any process in its territories of interest.exxonmobilchemicaltsl. damage. with the objective of bringing together. nor any endorsement of any product or process. footers.EM-4500 • MLPI • MTDP-3 • TransPlussm Scott A. . accuracy. and we expressly disclaim any contrary implication. We expressly disclaim liability for any loss. distribute. You may not copy this document to a Web site. ExxonMobil Chemical and IFP formed an Alliance called ParamaXsm. including all of its headers.Advanced MHAI . PxMax and XyMax are service marks of Exxon Mobil Corporation. disclaimers. For grass roots applications. the merchantability. We based the information on data believed to be reliable on the date compiled. but we do not represent. Ramsey Xylenes Licensing Manager scott. Figure 20 IFP . and other information. or any affiliates they directly or indirectly steward. “our”.Single Source Technology and Service Provider for Grass Roots BTX Aromatics Complexes IFP • • • • • • • • Reformer AromizingTM Hydrotreating ArofiningTM Eluxyl BTX Sulfolane Extraction* Morphylane Extractive Dist.

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