Zeolite Catalysts reduce the Aromatics Surplus in Refinery and Petrochemical Streams

Ernst O. Koehler, Sud-Chemie Inc., Louisville, KY, United States Abstract

Increasingly stringent regulations on aromatics in motor fuels will put tremendous pressure on refiners to cope with the surplus of aromatics. This situation will become particularly serious after the year 2005 when further reductions of aromatics in gasoline will come into force which can no longer be compensated for by simple process adjustments. A different process portfolio along with new catalyst solutions is required to cope with the future aromatics scenario. SUD-CHEMIE provides a great selection of zeolite based catalysts to the petroleum industry. This paper highlights four zeolites based catalysts and processes, respectively, that help the industry to convert aromatics to high value products or upgrade low value aromatics to valuable chemical intermediates. C5/C6 paraffin isomerization is a preferred process option to give refiners a relief on aromatics in gasoline. The zeolitic HYSOPAR catalyst can stand higher sulfur levels than conventional catalysts and converts benzene into other valuable gasoline components without sacrificing too much of octane. Pyrolysis gasoline will be a real burden in the future. However, it can be converted to high value paraffinic steam cracker feed with the ARINO process which is distinguished by 1st stage aromatics hydrogenation followed by zeolitic cracking and ring opening of naphthenes to paraffins in the 2nd stage. ARINO is a joint development of LINDE, SUD-CHEMIE and VEBA. Highly aromatic but low cetane middle distillates such as LCO can effectively be upgraded to valuable diesel blend stocks with the ASAT catalyst that provides HDAr along with HDS and HDN functions. Its sulfur tolerance (500 ppm) makes ASAT ideally suited for low cost 2-stage processing based on existing equipment. Upgrading of BTX aromatics to make chemical intermediates is gaining momentum in light of the expected up-cycle of the petrochemical industry around 2003. The zeolite based ISOXYL catalysts allow for more efficient p-xylene production with minimized xylene losses and by-product formation at higher space velocity than competitive catalysts. Based on its technological background and strong focus on zeolite catalysts, SUD-CHEMIE will continue to work on zeolite catalyst solutions for the refining and petrochemical industries. These include processes for environmentally friendly synfuels, free of aromatics, and alternative routes to make chemical intermediates such as olefins without aromatics as by-products.

Introduction
The following is an attempt to give an overview on some of the most versatile processes and drop-in catalyst solutions to resolve issues in connection with aromatics in the oil refining and petrochemical industries. The primary goal is to make economic use of aromatics by upgrading them to valuable streams rather than dumping aromatics into low value outlets such as fuel oil. Compliance with current and future regulations as well as with the market demand is a prerequisite for the justification of aromatics upgrading. Zeolite catalysts above any other structural group of catalytic materials have proven records in helping the oil processing industries through their shape selective function, combined with tailored acidity. A great variety of reactions can be triggered - the most common types are cracking, isomerization, polymerization and alkylation. The applications for advantageous use of zeolites, discussed in the sections below, are: Aromatics reduction in gasoline Upgrading of pyrolysis gasoline Aromatics reduction in middle distillates Upgrading of BTX aromatics

Aromatics Reduction in Gasoline Options for the Refiner

In all industrialized areas in the world, more stringent gasoline specifications are to come around the year 2005, bringing along tighter rules on sulfur and aromatics in particular (Table 1).
Europe 2000 60 150 1.0 18 42 2.7 Europe 2005 60 50 1.0 18 35 2.7 USA 2006 51.7 30/80 1.0 20 25-30 2.7 California 2003 48.2 20 0.8 6 25 2.2 Japan 2005 72 30? 1.0 10 ? 0.5

Specification RVP Sulfur Benzene Olefins Aromatics Oxygen

Unit kPa ppmw % Vol % Vol % Vol % Wt

Table 1 - Gasoline specifications The reduction of aromatics to 25-35 % Vol. or even further will impose a number of problems on refiners. It is foreseeable that the resulting surplus in aromatics cannot fully be accommodated by the chemical industry. Moreover, aromatics are high RON components, i.e. the lower octane in reformulated fuels needs to be compensated for by other high octane components, preferably from processes that can convert aromatics to high octane components. In Figure 1, several major refinery processes to improve RON are evaluated with regard to their compatibility with present and future regulations. These include isomerisation, reforming, addition of FCC-Naphtha, alkylation, addition of oxygenates or polygas or butanes. In light of the Californian ban on MTBE and future reduction of oxygenates in Japan, the most favorable options are alkylation and C5/C6 isomerisation, the latter in particular due to the straightforward nature of the process and low capital investment. In the future, isomerization of C7+ streams along with ring opening of aromatic compounds needs to be considered, too, to re-route these streams from reformers. Further octane compensation will come from C4 dimerization to iso-octane and alkylation. Zeolite catalysts are under development for both processes.
ation FCC Naph ta

Oxyg enat es

erate

ate

Alky late

Spec ific

Isom

Poly gas

Refo rm

RVP Benzene Aromatics Olefins Sulfur

negative

neutral

positive

Figure 1 - Process options to react on new gasoline specifications C5/C6 Isomerization can become of even greater importance in the future to fill the octane gap caused by deep desulfurization of FCC gasoline. The 10 ppm sulfur limit cannot be achieved without losing some high octane olefins due to hydrogenation. Subsequent product upgrading by isomerization is a viable option. A sulfur tolerant isomerization catalyst is highly desirable in this context.

Buta

nes

Benzene management with C5/C6 isomerization for high sulfur feedstocks

It is widely accepted that the most economic and octane effective route to reduce benzene is to eliminate benzene and benzene precursors from the naphtha reformer feed by prefractionation in an upstream splitter and send these precursors to an isomerization unit. With this approach benzene will be saturated and isomerized to a mixture of higher octane saturated cyclics. In the future, there will be a need for feed streams to isomerization to be composed of fractions from totally different sources, including those with a very high benzene content. To make up for octane losses and debottleneck the gasoline production, it is particularly attractive to feed light naphtha to the isomerization unit without pretreatment. Platinum promoted isomerization catalysts can handle benzene to an appreciable extent, however, only for feeds that are essentially free of sulfur. Conventional isomerization processes/catalysts cannot tolerate sulfur. In contrast, the commercially proven CKS ISOM, licensed exclusively by Kellogg Brown & Root and using SD-CHEMIEs HYSOPAR catalyst, can be applied to sulfur rich, untreated feeds1,2. Although the hydrogenation activity is dramatically inhibited with traditional isomerization catalysts when sulfur is present in the feedstock, even benzene saturation in the presence of about 50 ppm sulfur can be considered with this sulfur tolerant catalyst. As the HYSOPAR catalyst also hydrogenates sulfur compounds, CKS ISOM can help control benzene and sulfur with respect to future specifications, thus relieving the load on upstream naphtha hydrotreaters and reformers and making a positive contribution to the overall refinery economics. HYSOPARs superior performance under extreme conditions has been proven in CEPSAs 8000 BPSD isomerization unit at Algeciras, Spain which is based on CKS ISOM C5 recycle process technology1 . Figure 1 shows a plot of the records on sulfur in the liquid feedstock as well as in the recycle gas. The sulfur level in the naphtha feed averaged close to 100 ppmw with peak levels of up to 200 ppmw and the recycle gas contains similar amounts of sulfur on a volume basis, resulting in an average of about 150 ppmw of total sulfur. This is certainly a unique feature of HYSOPAR.

200

70

Feed
150

Recycle Gas
Outlet iC5/C5

65

Sulphur (ppm)

100

60

50

55

0
Jan 93 Aug 93 Mar 94 Sep 94 Apr 95 Oct 95 May 96 Dec 96 Jun 97 Jan 98 Jul 98

50 0 50 100 150 200 250 300 350 400

Total Sulphur (ppmw)

Figure 2 - CKS ISOM Unit at CEPSA, Algeciras/Spain, operating at very high sulfur levels Encouraged by the excellent commercial performance of HYSOPAR which includes experience with up to 5 wt% of benzene in the isomerization feed, a pilot plant program was conducted to check on the 2 catalysts ability to cope with up to 15 wt% of benzene, in particular at higher sulfur levels . As can be seen in Figure 3 (left), showing the cyclic C6s distribution at different WABT (weight -1 average bed temperature) at a liquid hourly space velocity of 1 h , complete saturation is achieved below a WABT of 120 C. This temperature was still sufficient to get 100% Bz conversion even at a liquid hourly space velocity as high as 4 h-1. Spiking the same feed with 30 ppm sulfur (as ethyl mercaptan) affects the hydrogenation activity for benzene to a certain extent, resulting in a need for higher reaction temperatures to complete benzene hydrogenation. However, WABTs are still close to equilibrium at 260 C, i.e. the impact of sulfur on the isomerization function is not pronounced.

Cyclic C6 Composition (wt %)

16 14 12 10 8 6 4 2 0 120 130 140 150 160 170 180 190 200 210 220 230 240 250 Bz CH MCP
16 14 12 10 8 6 4

Cyclic C6 Composition (wt %)

Bz CH MCP

cycC6
Feed : 15 % Bz + 85 % n-C5

cycC6
Feed: 15 % Bz + 85 % n-C5 + 30 ppm S 100 120 140 160 180 200 220 240 260

2 0

Reactor WABT (C)

Reactor WABT (C)

Figure 3 - Effect of Benzene: Sulfur-free feed (left) and sulfur-rich feed (right) As demonstrated in Figure 4, HYSOPAR is an efficient hydrodesulphurization (HDS) catalyst under these conditions, despite the effect of sulfur on benzene hydrogenation activity. The HDS reaction is completed at about 160 C. Provided that enough H2S can be purged from the process gas, HYSOPAR can be used to reduce sulfur in untreated naphtha streams.

100 80

% HDS

60 40 20 0 100 120 140 160 180 200 220 240 260 Feed : 15 % Bz + 85 % n-C5 + 30 ppm S

Reactor WABT (C)

Figure 4 HYSOPAR converts sulfur in naphtha effectively Apparently, HYSOPAR is more successful than competitive catalysts in retaining the basic functions required for isomerization of a feedstock containing up to 15 wt% benzene in combination with large amounts of sulfur. The unique characteristics of the HYSOPAR catalyst in the CKS ISOM process open up new opportunities to directly process virgin naphtha from atmospheric distillation along with benzene and benzene precursors extracted from reformer feeds. This can eliminate the need for a separate naphtha hydrotreater as well as separate downstream processing of benzene such as hydrogenation with noble metal or nickel catalysts. This means considerable capital savings and lower operating costs. Furthermore, HYSOPAR provides an attractive tool in making up for octane losses from lower benzene in the gasoline pool, even under unfavorable conditions like high sulfur feeds.

Upgrading of Pyrolysis Gasoline

A main source of the aromatics surplus is the heavy pyrolysis gasoline, a by-product of the production of ethylene and propylene from naphtha steam cracking. Due to the predicted worldwide increasing demand for ethylene and propylene the surplus of heavy pyrolysis gasoline will increase further. This will create a major driving force to convert heavy pyrolysis gasoline into products of higher value and better environmental compatibility. Sud-Chemie, together with Linde and VEBA OIL, jointly developed a novel technology for upgrading of low value aromatic streams to high value steamcracker feedstock - the ARINO technology. ARINO is distinguished by its high selectivity to C2C4 n-alkanes which are the most effective feed components with respect to high ethylene and propylene yields.

10 9 8 7 6 5 4 3 2 1 0

14.0

Annual Growth (%)

Ethylene

Source: CMAI, Mar-99

Growth Rate (%)

12.0 10.0 8.0 6.0 4.0 2.0

Propylene

91

92

93

94

95

96

97

98

99

'00

'01

'02

'03

0.0 West Europe North America Middle East

World Real GDP Growth

World Ethylene Demand Growth

Figure 5 World ethylene growth and propylene growth per gegion

The ARINO Technology comprises two catalytic reaction steps and a cryogenic product recovery. In the first step aromatics are hydrogenated to naphthenes in a conventional multi-bed hydrogenation reactor, followed by a ring opening and cracking reactor in the second step5-7. This stage uses a novel pentasil (MFI) based catalyst with palladium loading. In contrast to typical bi-functional catalysts, the ARINO cracking catalyst is distinguished by its low palladium content of max. 0.1 wt%6. Palladium content, Brnsted acidity and the nature/content of binder are crucial parameters for the ring opening and cracking reaction8.

H2 C2A/B A/B A/B H2 A/B HD Cold Box RGV C2+ LPG Ofen

A/B PSA

C7+

PySBi

Figure 6 Possible schematic of the ARINO process [courtesy LINDE AG] The main challenge in this process is to maximize the yield of C2C4 n-alkanes while keeping the formation of methane and aromatics at the lowest possible level. Low to moderate Pd content favors high C2C4 n-alkane yields at low formation of methane and aromatics. Even though an increase in palladium leads to improved C2C4 n-alkane yield as well as lower aromatics make, there is a trade-off in terms of higher methane formation which adversely affects the process economics. The C2C4 nalkane fraction predominantly consists of propane (60%) as well as smaller amounts of ethane and butane. The Brnsted acidity plays a significant role in achieving excellent C2C4 n-alkane yields as well as low formation of methane and aromatics. Figure 7 shows three different MFI-types that are mainly distinguished by different acidity and their effect on liquid conversion and product distribution. Interestingly, the C2C4 n-alkane fraction indicates different yields on propane and ethane but no significant change in butane as a function of the zeolite acidity.

Hydrocarbon yields [wt%]

Liquid conversion [%]

100 90 80 70 60 50 40 30 20 10 0
e an et h

MFI-1

MFI-2

MFI-3

ne

5+

ne

es

at ic s

e an pr op n-

ka

an

th en

ha

nal

ut

ar om

i-b

2C 4

Conversion

Product distribution

na

ph

C2-C4 n-alkane distribution

Figure 7 - Effect of the zeolite acidity on liquid conversion and product distribution While the nature of the zeolite plays a significant role for the process, the chemistry of the binder is of lesser importance. Conversion and product slate are surprisingly close for all binders tested in conjunction with MFI-2 zeolite. However, some binders showed a slightly better C2C4 n-alkane yield and lower formation of methane and aromatics than others.
100 90 Yields aromatics C2-C4 n-alkane methane 100 90 80

Hydrocarbon yield [wt%]

80 70 60 50 40 30 20 10 0 250

bu

et

ta

ne

60

Conversion
liquid i-propylcyclohexane methylcyclohexane ethylcyclohexane

50 40 30 20 10 0

280

310

340

370

400

Inlet temperature [C]

Figure 8 Effect of temperature on conversion and product distribution Operating conditions and reactor temperature in particular have a significant effect on the catalyst performance (Figure 8). In the range of 280 to 370C the liquid conversion increases rapidly from 20 % to 80 %. Above 370C the curve becomes flat. With regard to C2C4 n-alkane yield as well as low formation of methane and aromatics, the best performance is achieved at 370C. Higher temperatures lead to an increase in C2C4 n-alkanes and lower aromatics. However, there is a major drawback in terms of high methane make at elevated temperatures. The conversion of naphthenes largely depends on the C-number, e.g. the iso-propylcyclohexane conversion is always lower than the conversion of methylcyclohexane and ethylcyclohexane and approaches zero at 280. After successful optimization of catalyst and process parameters, ARINO is now ready for commercialization. The Pd-MFI catalyst works perfectly for the cracking and ring opening of hydrogenated heavy pyrolysis gasoline to produce valuable steam cracker feed. High liquid conversion and C2C4 n-alkane yields are achieved at low formation of methane and aromatics, properties that are crucial for an economic process.

Aromatics Reduction in Middle Distillates

Two major trends are going to change the refinery world to an extent that has never been observed at any point in the refining history:

Conversion [%]

70

First, all over the world, the demand for diesel fuel is steadily on the increase while markets for residual fuel oil are dramatically shrinking. The imbalance caused by this trend towards higher quality products can only be compensated for by process technologies which provide upgrading capabilities for low value hydrocarbon fractions. Second, tighter specifications on middle distillates will impose further burdens on refiners in terms of considerable amounts of capital investments. It has become apparent that catalysts and processes which are currently employed in diesel production will not be able to meet future specifications , especially in terms of sulfur content (10/50 ppm) and poly-aromatics (1 wt%), not to mention the proposed high cetane numbers. Furthermore, density and end point reduction will call for a shift towards the use of lighter fractions. Alternative feed streams need to be made available to make up for the lower boiling fractions going into diesel fuel. First candidate is LCO from Fluid Catalytic Cracking. In view of the decreased demand for fuel oils where LCO is normally going to, refiners will have to blend more LCO into their diesel. However, blend stocks containing large amounts of aromatics such as LCO and visbreaker gas oil are distinguished by a low cetane number, hence requiring severe post-processing.

SD-CHEMIE has recently introduced a new highly sulfur tolerant dearomatization catalyst under the name of ASAT. This catalyst provides outstanding capabilities for LCO upgrading. ASAT allows for a totally new concept by using existing hydrotreaters as a first stage unit without any modifications and processing a 500 ppm sulfur stream in the second stage dearomatization (ASAT) reactor. This novel concept can not only remove poly-aromatics completely and reduce total aromatics down to a few percent, but simultaneously is capable of achieving sulfur levels below 10 ppm and fully converts 9,10 organic nitrogen compounds .

Catalyst Performance
ASAT is ideally used in a second stage dearomatization reactor as an add-on to existing hydrotreaters, making diesel according to the 500 ppm specifications. Due to its tremendous hydrogenation power, treatment with ASAT can result in a dramatic reduction of total aromatics to a level very close to equilibrium which is limited by temperature. The results exhibited in Figure 9 were achieved with pre-treated LCO of 42,5 wt% total aromatics which are reduced to 3,3 wt% at moderate temperature (327 C). Poly-aromatics have vanished completely and are no longer detectable under those conditions.

50 Concentration, wt % 40 30 20 10 0 Feed 307 315 327 Concentration, wt ppm Total Aromatics Poly Aromatics

500 400 300 200 100 0 Feed 307 315 327 Sulphur Nitrogen

Temperature, C

Temperature, C

Figure 9 Dearomatization and HDS/HDN performance versus temperature Conditions: P = 62 barg, H2/HC = 712 Nm3/m3, LHSV = 1 h-1 Figure 9 also shows the catalysts ability to hydrogenate difficult-to-treat-sulfur as well as nitrogen compounds. A temperatures of 315 C is sufficient for ultra deep HDS to < 10 ppm sulfur in the product. The absence of nitrogen compounds at all conditions is an excellent basis for color stability. The product from processing with ASAT has the distinguished properties of a valuable blending stock. Table 2 summarizes typical operating conditions for Light Cycle Oil (LCO) and Light Gas Oil (LGO), respectively, as well as the feed and product properties. While ASAT needs moderately

severe conditions in terms of temperature, pressure and hydrogen supply to get down to zero level in poly-aromatics with the highly aromatic LCO feed, LGO can be effectively treated at temperatures in the range of 280- 290 C and pressure as low as 45 barg. Tremendous improvements are achieved for LCO with regard to gravity (+9 API) and Cetane Index (+10). Sulfur is below the toughest diesel specifications (< 10 ppm) and nitrogen is totally converted. The aromatics removal also causes an appreciable shift in the T95 point by 13 C (LCO), hence shifting more product into the diesel boiling range. LGO feed with much lower aromatics, treated at less severe operating conditions, shows a less pronounced shift in T95 of 5 C.
LCO Case Operating Conditions Pressure Temperature H2/Oil LHSV Properties Gravity Total Aromatics Polyaromatics Sulfur Nitrogen Cetane Index [D-4737] T95 Gas Make Liquid Yield [C] [wt%] [vol%] Unit [barg] [C] [Nm3/m3] [hr-1] Unit [API] [vol%] [vol%] [ppm] [ppm] Feed 31.6 42.5 15.1 400 127 41 359 100 62 315 712 1.0 Prod 40.6 2.5 0 9 0 51 346 0.2 105.5 Feed 39.6 26 2.4 260 8 361 100 45 288 535 1.2 Prod n.d. 0 6 0 356 0.4 103.2 LGO Case

Table 2 - Operating conditions and feed/product properties Although the catalyst's acidic function has caused ring openings and the formation of some lighter components, there is hardly any gas make, i.e. liquid product loss. There is rather an appreciable gain in liquid volume yield which is highest with LCO due to the conversion of high density aromatic compounds to lower density naphthenes and some paraffins. Overall, the results discussed above are a clear proof of ASATs superiority over state-of-the-art catalysts which can only survive sulfur upsets on a temporary basis, yet such incidents are devastating to their dearomatization performance and these catalysts would need several days to recover the hydrogenation activity11.

Process Options
Due to the lack of sulfur tolerance, existing dearomatization technologies are based on multi-stage processing to provide low sulfur feed with typically < 50 ppm sulfur to the dearomatization reactor (Figure 10).
Conventional Process S=50ppm Gas Oil Blend
ASATTM vs Conventional Hydroprocessing
S=50ppm

2005 Diesel

Conventional HDS Conventional:

Conventional HDS

Gas Oil Blend

Deep HDS

Deep HDS
Deep HDAr

2005 Diesel

Deep HDAr

ASAT Process

S=500ppm Gas Oil Blend 2005 Diesel

Gas Oil Blend

ASAT:

Conventional HDS

S=500ppm

ASAT &
Deep HDAr

Deep HDS

Sulphur < 50 ppm Nitrogen < 5 ppm Tot.Arom. < 10%wt. PNA < 1%wt. SG < 825 kg/m3 T95 < 340C Cetane > 58

2005 Diesel

ASAT Conventional HDS Deep HDS & Deep HDAr

Figure 10 - ASAT Process scheme vs conventional hydroprocessing

This means high investment cost, creating a hurdle to refiners to adapt their process portfolio to future requirements. The basic idea behind ASAT is to provide a catalyst for a simple two-stage process whereby the ASAT reactor can be fed with gas oil of 500 ppm sulfur. Thus the addition of a second stage HDAr reactor to an existing (conventional) hydrotreater will result in a product that meets all current and future specifications. This can be accomplished with very inexpensive revamps using existing equipment. An interstage clean-up of the process gas to the HDAr reactor is recommended to achieve optimum dearomatization performance. ASAT can also be used advantageously in multi-reactor systems which incorporate mild hydrocracking and dewaxing, besides hydrodesulfurization. This enables refiners to flexibly adapt their hydroprocessing capabilities to future product specifications and changing feedstock requirements.

Benefits from ASAT

The application of ASATTM to LCO upgrading manifests the following performance features: Aromatics conversion close to equilibrium Increase of cetane Index: +10 Reduction of boiling point: > 10 C Considerable gain in liquid product volume Low gas-make Reduction of sulfur from up to 500 ppm to a few ppm Reduction of nitrogen from up to 200 ppm to zero ppm Current catalyst options require low sulfur content feed stocks to affect aromatics hydrogenation by a multi-stage process with deep desulfurization in the first stage(s). ASAT provides a simple, cost effective solution as it incorporates the existing HDS reactors without any modification as the first stage. This saves the installation of additional HDS capacity or even investment into a grass-roots unit. ASAT not only offers an economically viable solution but provides a flexible tool to refiners to meet all future specifications on middle distillates.

Upgrading of BTX aromatics

Although aromatics still are indispensable as high octane components in motor fuels, it is obvious that their contribution to the gasoline pool will shrink due to the tighter regulations. Benzene is a proven trigger of cancer in bio-organisms, aromatics in general form toxic combustion products and generate soot in the off-gas. However, the main sources of aromatics catalytic reformers and steam crackers are closely inter-linked with the production of refining products and olefins, respectively, so that their aromatics efficiency can only be reduced to a minor extent. It is widely accepted that this will increase the pressure on the markets and the need for processes that are capable of upgrading BTX and heavier aromatics to higher value products. Zeolites play an outstanding role in the conversion (and separation) of aromatics. The ARINO process with its zeolitic cracking catalyst (see above) destroys aromatics by converting them to paraffins by hydrogenation and ring opening. Yet, the majority of zeolite based processes is tailored to remove, shift, add or transfer alkyl groups in a very selective manner so that higher value aromatics are produced with high efficiency (Table 4).
Process Alkylation Alkylation Alkylation Isomerization Disproportionation Methylation Transalkylation Reactants benzene + ethylene benzene + propylene benzene + C10-C14 olefins mixed xylenes toluene toluene + MeOH C9+ aromatics Product ethylbenzene cumene linear alkyl benzenes p-/o-xylene xylenes + benzene p-xylene xylenes + benzene SUD-CHEMIE Zeolite/Catalyst EBEMAX CA-131 (non-zeolitic) development Product ISOXYL TDP-1 custom TRANSMAX

Table 4 Zeolite based aromatics processes and related SUD-CHEMIE products

The alkylation of toluene with methanol is not yet an industrial process but on the verge of commercialization. Figure 11 shows how above processes tie in with the overall scheme of aromatics processing. SUD-CHEMIE covers all process options marked grey with own zeolite catalysts or zeolite products used by third parties for own catalysts. The main advantages associated with zeolite based processing are the high selectivity toward the target product and low by-product formation. In the following, two applications are highlighted where advanced zeolite catalysts take advantage of these properties, hence providing superior process economics.
AROMATICS PROCESSING
C6Reformate C6+ Non-Aromatics
Hydrogenation Hydrogenation

Benzene Removal Benzene Removal

Gasoline Cyclohexane

Aromatics Aromatics Extraction Extraction

Alkylation of Alkylation of Propylene Propylene

Benzene
Clay Treating Clay Treating

Cumene

C7-

Alkylation of Alkylation of Ethylene Ethylene

Ethylbenzene
Dehydrogenation Dehydrogenation

Pygas
Selective Selective Hydroprocessing Hydroprocessing

Toluene Toluene Disproportion. Disproportion. Disproportion. Toluene Toluene Methylation Methylation Xylene Xylene Isomerization Isomerization
C9+

Styrene Ethylbenzene Ortho-Xylene Para-Xylene

C9+A C9+A Transalkylation Transalkylation

Purification of TA Purification of TA

PTA

Figure 11 Zeolite catalysts (marked grey) in the context of aromatics processing

Improved Economics from new Generation of Xylene Isomerization Catalysts

The isomerization of mixed xylenes to predominantly produce p-xylene is one of the most important processes for upgrading BTX streams to more valuable chemical intermediates. With an annual 12 growth rate of 6-8 % , para-xylene has still one of the highest growth rates of all chemical intermediates and after a period of over-capacity and low margins from p-xylene, the turnaround is expected in 2003. Also, the more stringent regulations on gasoline will create a need to process more C8 aromatics from reforming and pyrolysis gasoline in particular. This scenario creates a need for catalysts that enable p-xylene producers to get more product out of existing facilities in order to meet the processing requirements and improve profitability. It is generally accepted that EB dealkylation is preferable over so-called EB isomerization due to better economics. However, many EB dealkylation units are limited in throughput due to low activity catalysts. Catalysts with higher activity could raise the throughput and hence para-xylene production and profitability. Alike, revamps of EB isomerization to EB dealkylation could greatly benefit from high activity catalyst solutions. SUD-CHEMIE has developed tailor-made advanced MFI catalysts for virtually every EB dealkylation process established in the market, now offered under the name of ISOXYL: low pressure vapor phase isomerization (non-H2) high pressure/low temperature liquid phase isomerization (non-H2) medium pressure isomerization (H2) high pressure isomerization (H2) ISOXYL LPN ISOXYL HPN ISOXYL MPH ISOXYL HPH

10

For the most widespread medium pressure isomerization, SD-CHEMIE just completed a comprehensive development program on a new generation of ISOXYL MPH catalysts that can substantially improve plant economics by higher space velocity, higher EB conversion and lower xylene loss compared to other state-of-the art catalysts13. This has been achieved by careful optimization of all crucial catalyst parameters such as metal loading, SiO2/Al2O3-ratio and crystal size/shape of the MFI zeolite, binder, forming, etc. Furthermore, selectivation by silanization and coking as well as a novel proprietary selectivation method are available to ISOXYL MPH users. The new catalysts exceed all expectations in terms of xylene loss and EB conversion. Lower than usual by-product formation results in excellent xylene and benzene purity.
100 EB Conversion, % 90 80 70 60 50 390 C 380 C 360 C 340 C 0 1 2 3 4 400 C PXATE, % 110

Feed
105

EB (10 wt%) m-Xylene (90wt%) Operating Conditions LHSV=6.0 h-1, H2/HC=3.0 mol/mol, P=8 barg
340 360 380 400 420

100

SD-CHEMIE Proprietary Selectivation Method 95 Optimized Coke-Selectivation

90

320

Xylene Loss, wt%

Temperature, C

Figure 12 Outstanding performance with Sd-Chemies proprietary selectivation method The results in Figure 12 clearly indicate that especially SUD-CHEMIE's novel selectivation technique leads to outstanding activity and selectivity which is superior to optimized coke selectivation. Temperatures as low as 340-360C are required for EB conversion of 60-70%. Xylene losses are kept well below 1% at EB conversion up to 80% and even in case of 100% EBC, XL does not exceed 3 wt%. PXATE slightly increases with higher temperatures and is between 101 and 102 % throughout the temperature range. The newly developed selectivation method is also convincing in terms of by-product formation (Figure 13). C9+ formation is by a factor of three lower compared to coke selectivated catalyst and becomes more pronounced only for EB conversion approaching 100 %. Toluene make is slightly lower compared to pre-coking with a maximum at 380 C. The decrease at EBC > 90% can be explained by dealkylation/transalkylation of toluene prevailing at temperatures in the range of 400 C. Dealkylation of all aromatics at high temperatures also leads to elevated saturates make which is, however, not relevant to regular operations.
3,0 C9+ in Product, wt% 2,5 2,0 1,5 1,0 0,5 0,0 340 360 380 390 400 Proprietary Selectivation Toluene in Product, wt% Coke Selectivation 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 340 360 380 390 400

3,5 Saturates in Product, wt% 3,0 2,5 2,0 1,5 1,0 0,5 0,0 340 360 380 390 400

Temperature, C

Temperature, C

Temperature, C

Figure 13 Low by product formation from selectivated ISOXYL MPH catalysts While the high high activity and selectivity to p-xylene help to maximize plant utilization by higher than usual space velocity, ISOXYL MPHs low by-product formation (C9+, toluene, saturates) allows for achieving excellent xylene and benzene purity. Undoubtedly, SUD-CHEMIE's long-term experience as

11

a world-scale zeolite catalyst manufacturer greatly helped to develop xylene isomerization catalysts that help the petrochemical industry to better cope with C8 aromatics in the future. The new generation of ISOXYL MPH catalysts primarily focuses on upgrading of existing units by simple catalyst replacements as a cost-effective solution but will also be available as a licensed product for revamps and grass-roots units within an alliance with a reputable engineering and licensing partner.

Conclusions
The above is just a selection out of a great variety of sophisticated zeolites and catalysts from SDCHEMIE. However, they are good examples for the tailoring of zeolite based processing of aromatics. Thanks to zeolite catalysts like HYSOPAR, ARINO, ASAT and ISOXYL, the refining and petrochemical industries will have all the flexibility they need to cope with the aromatics surplus in light of future scenarios where alternative outlets and/or more efficient processing of aromatics will be a must. However, re-routing and upgrading of aromatics will not be enough to achieve a balanced supply and demand situation in the longer run. Therefore, alternative processes that avoid aromatics will be required. Fischer-Tropsch based gas to liquids (GTL) processes and related zeolite based downstream processing for either synfuels or chemical intermediates will find receptive markets. SUDCHEMIE already now is the catalyst supplier to the largest synfuels plant in the world (COD process at Mossgas refinery in South Africa) and is together with licensing partners - deeply engaged in the methanol to olefins processing with zeolite catalysts. This paper would not have been possible without direct and/or indirect contributions from many colleagues and co-workers. The author would like to thank the following people in particular and apologizes to those who should be mentioned but are not listed below: P.Miro and M.Perez of CEPSA for their research work on benzene saturation with HYSAPAR. My colleagues C.Ringelhan, V.Kurth, G.Burgfels, J.G.Neumayr, W.Seuffert and J.Klose for the ARINO research work. My retired colleague D.Huang for the ASAT research work. My colleagues G.Burgfels, J.Osbourne, P.Roeger and H.Takeda for the ISOXYL research work.

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