Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 2.7

UOP TATORAY PROCESS

Antoine Negiz and Thomas J. Stoodt
UOP LLC Des Plaines, Illinois

INTRODUCTION
An aromatics complex is a combination of process units which are used to convert petroleum naphtha and pyrolysis gasoline to the basic petrochemical intermediates: benzene, toluene, and xylenes (BTX). Details of the aromatic complex are discussed in greater depth in Chap. 2.1. A fully integrated modern complex designed to produce benzene, paraxylene (PX), and sometimes ortho-xylene includes UOPs Tatoray process. A simplified flow diagram of a typical aromatics complex designed for maximum production of PX is shown in Fig. 2.7.1. The Tatoray process is integrated between the aromatics extraction and xylene recovery sections of the plant (Fig. 2.7.1). Toluene (A7) is fed to the Tatoray unit rather than being blended into the gasoline pool or sold for solvent applications. If the goal is to maximize the production of PX from the complex, the C9 aromatic (A9) by-product can also be fed to the Tatoray unit rather than blending it into the gasoline pool. Processing A9-A10 in a Tatoray unit shifts the chemical equilibrium in the unit toward decreased benzene production and increased production of xylenes. The Tatoray process provides an ideal way of producing additional mixed xylenes from low-value toluene and heavy aromatics. What is seldom recognized, however, is where the xylenes are produced within the complex. For an aromatics complex that includes transalkylation, approximately 50 percent of the xylenes in the complex come from the transalkylation reaction, that is, the Tatoray process. The reformate provides approximately 45 percent, and 5 percent comes from C8 aromatic isomerization such as the Isomar process, via conversion of ethylbenzenes to xylenes. The Tatoray process produces an equilibrium mixture of xylenes plus ethylbenzene. The xylenes are recovered and isomerized to PX while the ethylbenzene can also be converted to xylenes. The incorporation of a Tatoray unit to an aromatics complex can more than double the yield of PX from naphtha feedstock. It is extremely important, when looking at improving xylene production economics, that one focus not only on the reformer, but also on the transalkylation process and its performance. There are a number of different strategies that producers are pursuing to increase profitability. Two in particular are to reduce feedstock consumption (and the associated cost) and upgrade by-products to increase their sale value. Transalkylation can play a key role in both strategies.

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UOP TATORAY PROCESS 2.56

BASE AROMATICS PRODUCTION PROCESSES

Extraction Reformate Splitter

Raffinate Benzene Bz Col Tol Col A9 Col

Platforming

NHT Tatoray Naphtha Parex Xylene Splitter OX Column Isomar ortho-xylene DeHept Column A10+ para-xylene Light Ends

FIGURE 2.7.1

Typical UOP aromatics complex.

PROCESS CHEMISTRY
The two major reactions in the Tatoray process, disproportionation and transalkylation, are illustrated in Fig. 2.7.2. The conversion of toluene alone to an equilibrium mixture of benzene and xylenes is called disproportionation. The conversion of a blend of toluene and A9 to xylenes through the migration of methyl groups between methyl-substituted aromatics is called transalkylation. In general, both reactions proceed toward an equilibrium distribution of benzene and alkyl-substituted aromatics. Methyl groups are stable at Tatoray reaction conditions, and thus the reaction equilibrium is easy to estimate when the feed consists of all methyl-substituted aromatics. The equilibrium distribution is illustrated in Fig. 2.7.3. The reaction pathways involving A9 for the Tatoray process have also been described elsewhere.1 More complex reaction pathways occur when other alkyl groups are present in the feed. The Tatoray process effectively converts the ethyl, propyl, and higher alkyl group substituted A9-A10 to lighter single-ring aromatics via dealkylation, while preserving the methyl groups. The lighter, mostly methyl-substituted, aromatics proceed with transalkylation to produce benzene and xylenes in a yield pattern governed by equilibrium. The dealkylation reactions involving propyl and higher substituted groups typically proceed to completion. It is also known that the diffusion coefficients of ethyl and higher alkyl group substituted rings in some aluminosilicates are much lower than those of the methyl-only substituted rings.2 The Tatoray catalyst enhances the transport properties of the reactants, thereby increasing the reaction efficiency. The TA series of catalysts was first commercialized in 1969. A new generation has been introduced, on average, every 6 years. UOP introduced TA-4 in 1988. Tatoray licensees are very familiar with TA-4 catalyst and have experienced its ruggedness and ability to handle a wide variety of operating conditions while maintaining performance. The catalyst demonstrates superior selectivity and stability over a wide range of feed rates and feed compositions. High per pass conversion to benzene and mixed xylenes established TA-4 as economically attractive.

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Disproportionation C 2 Toluene Transalkylation C + C C Toluene C9 Aromatics

FIGURE 2.7.2 Major Tatoray reactions.

C + Benzene C Xylenes

C 2

C Xylenes

100 Equilibrium Concentration, mol-% 80 60 40 Toluene 20 Benzene 0 1 1.2 1.4 1.6 1.8 2

A11+ Tetramethylbenzenes Trimethylbenzenes Xylenes

2.2

2.4

2.6

2.8

Methyl/Phenyl Ratio in Feed

FIGURE 2.7.3 Equilibrium distribution of methyl groups at 700 K.

The most recent Tatoray catalyst to be successfully commercialized is called TA-5.3 This catalyst was designed as a drop-in reload catalyst for service in the Tatoray process and was commercialized in October 2000. The stability of TA-5 catalyst is more than double that of TA-4. This results in improved on-stream efficiency and a reduction in regeneration frequency. Commercial units have also shown that the activity of TA-5 is at least 50 percent better than that of TA-4, allowing users to potentially increase throughput while maintaining current cycle lengths. Alternatively, users can use the TA-5 catalyst to process heavier aromatic feeds to produce higher-value benzene and mixed-xylenes products. Figure 2.7.4 illustrates the relative performance of TA-5 versus TA-4 in terms of activity and stability. This information is based on data from a commercial unit that has been running with TA-5 since October 2000. Prior to the reload of TA-5 catalyst, this unit was loaded with TA-4. This unit has continuously processed significantly more feed at a substantially lower hydrogen/hydrocarbon mole ratio.

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UOP TATORAY PROCESS 2.58

BASE AROMATICS PRODUCTION PROCESSES

Average Rx Bed Temperature, C

TA-4 Slope = X

Slope = 0.5X

TA-5

Catalyst Life (MT of Feed/kg of Catalyst)

FIGURE 2.7.4 TA-5 stability and activity.

TA-5 catalyst provides significant advantages over other catalysts:

Higher stability. Figure 2.7.4 clearly illustrates the stability of TA-5 catalyst versus TA4 catalyst. The slope of the curves shows TA-5 catalyst to be twice as stable as TA-4 catalyst. This means a reduction in regeneration frequency that results in improved on-stream efficiency. Higher activity. The 50 percent higher activity translates to increased throughput or lower hydrogen to hydrocarbon ratios while maintaining the same cycle length. Alternatively, the amount of heavy aromatics charged to the Tatoray unit can be increased to maximize PX production from the complex while maintaining stability. No process modification required. With the same throughput across the reactor, at the same operating pressure levels and H2/HC ratio as TA-4 catalyst, no process modifications are required to use TA-5 catalyst. High conversion and high yield. TA-5 catalyst provides the high conversion and yields obtained using TA-4 catalyst. Contains no precious metals. The TA-5 catalyst contains no precious metals. Benzene purity. The quality of the benzene produced depends on the feed composition. In many applications, TA-5 catalyst delivers high quality benzene product which does not require purification by extraction. Regenerability. It shows complete recovery of activity, yields, and stability. UOPs commercial experience and technical support. UOPs commercial experience, comprehensive guarantees, technical service, and state-of-the-art research facilities ensure that the customer will achieve optimal catalyst performance of the Tatoray process unit. The experience gained from the large installed capacity and the success of the TA series catalysts installed in these units help ensure that future reloads will also be a success.

DESCRIPTION OF THE PROCESS FLOW

The Tatoray process uses a very simple flow scheme consisting of a fixed-bed reactor and a product separation section (Fig. 2.7.5). The fresh feed to the Tatoray unit is first com-

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Light Ends Feed Surge Drum Heater Reactor C9 Aromatics Toluene Recycle Gas To BT Fractionation Section Makeup H2
FIGURE 2.7.5 Tatoray flow diagram.

Product Separator Purge Gas Stripper Overhead Liquid

bined with hydrogen-rich recycle gas, preheated by exchange with the hot reactor effluent, and then raised to reaction temperature in a fired heater. The combined feed vapor is then sent to the reactor where it is processed downflow over a fixed bed of catalyst. The reactor effluent is then cooled by exchange with the combined feed and a product condenser and is sent to a product separator. Hydrogen-rich gas is taken off the top of the separator, where a small portion of it is purged to remove accumulated light ends from the recycle gas loop. It is then mixed with makeup gas and recycled to the reactor. Liquid from the bottom of the separator is sent to a stripper column. The overhead from the stripper is cooled and separated into gas and liquid products. The stripper overhead gas is exported to the fuel gas system. The overhead liquid is recycled to the Platforming unit debutanizer column so that any benzene in this stream may be recovered to the extraction and or in the BT separation section of the aromatics complex. The benzene and xylene products, together with the unreacted toluene and C9 aromatics, are taken from the bottom of the stripper and recycled to the BT fractionation section of the aromatics complex. Because of the dealkylation reaction pathway, the reactor section of the Tatoray process is maintained in a hydrogen atmosphere even though no net hydrogen is consumed in the transalkylation reactions. In practice, a small amount of hydrogen is always consumed due to the dealkylation side reactions. Hydrogen consumption increases for heavier feedstocks since these generally contain heavier alkyl groups, typically C3 and C4.

FEEDSTOCK CONSIDERATIONS
The feed to a Tatoray unit is typically a blend of toluene and A9-A10 derived from reformate. UOP also has experience with pygas-derived A9-A10 blends with reformate. Figure 2.7.6 shows typical yields on fresh feedstocks ranging from 100 wt % toluene to 100 wt % A9. As shown in Fig. 2.7.6, the product composition shifts away from benzene and toward xylenes as the A9 concentration in the feed increases. Saturates in the feed are generally cracked to propane and butane. For this reason, a limitation on saturates in the feed

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UOP TATORAY PROCESS 2.60

BASE AROMATICS PRODUCTION PROCESSES

100 Overall Product Yield, wt-% of Fresh Feed Benzene + Xylenes 80 60 40 Benzene 20 0 0 20 40 60 80 100 C9 Aromatics in Fresh Feed, wt-%
FIGURE 2.7.6 Tatoray yield structure as a function of A9 concentration in feed.

Xylenes

is usually specified. In general, feed to a Tatoray unit should meet the specifications outlined in Table 2.7.1.

PROCESS PERFORMANCE
The ability to process A9-A10 in a Tatoray unit can make more feedstock available for xylenes production and dramatically shifts the selectivity of the unit toward decreased benzene and increased production of xylenes. A typical aromatics complex without a Tatoray unit can produce approximately 200,000 MTA of PX from 25,000 BPD of Light Arabian naphtha (160 to 300F ASTM Distillation). If a toluene-only Tatoray unit is added to the complex, the same 25,000 BPD of naphtha can produce 280,000 MTA of PX, an increase of 40 percent. When an A7/A9-A10 Tatoray unit is added to the complex, the endpoint of the feed naphtha can be increased from 300 to 340F in order to maximize the amount of A9A10 precursors in the feed. If we keep the feed rate to the reformer constant, 25,000 BPD of this heavier naphtha will produce about 420,000 MTA of PX, an increase of 110 percent over the base complex (Fig. 2.7.7). The maximum theoretical conversion per pass is limited by equilibrium and is a function of the feedstock composition. For example, theoretical conversion for a pure toluene feed is approximately 59 wt % per pass. Operating at high conversion minimizes the amount of unconverted material that must be recycled through the BT fractionation section of the complex. A smaller recycle stream minimizes the size of the benzene and toluene columns, minimizes the size of the Tatoray unit, and minimizes the utility consumption in all these units. Tatoray units are designed and operated to provide a range of conversions, depending on desired production rates, feedstock and utility values, and capital sensitivity.

EQUIPMENT CONSIDERATIONS
Because the Tatoray process uses relatively mild operating conditions, special construction materials are not required. The simplicity of the process design and the use of conventional

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FIGURE 2.7.7

Maximum para-xylene yield with Tatoray.

metallurgy result in low capital investment and maintenance expenses for the Tatoray process. The simple design of the Tatoray process also makes it ideal for the conversion of existing reformers, hydrodealkylation units, and hydrotreaters to Tatoray service. To date, two idle reforming units, two hydrodealkylation units, and one hydrodesulfurization unit have been successfully converted to service as Tatoray units. The charge heater is normally a radiant-convection-type heater. The process stream is heated in the radiant section, and the convection section is used for a hot-oil system or for steam generation. The heater can be designed to operate on either fuel gas or fuel oil, and each burner is equipped with a fuel-gas pilot. A temperature controller at the heater outlet regulates the flow of fuel to the burners. Radiant-section tubes are constructed of 1.25% Cr and 0.5% Mo. Tubes in the convection section are carbon steel. The Tatoray process uses a simple downflow, fixed-bed, vapor-phase reactor. The reactor is constructed of 1.25% Cr-0.5% Mo. The purpose of the product separator is to split the condensed reactor effluent into liquid product and hydrogen-rich recycle gas. The pressure in the product separator determines the pressure in the reactor. Product separator pressure is regulated by controlling the rate of hydrogen makeup flow. Hydrogen purity in the recycle gas is monitored by a hydrogen analyzer at the recycle gas compressor suction. When hydrogen purity gets too low, a small purge is taken from the recycle gas. The product separator is constructed of killed carbon steel. The recycle gas compressor is usually of the centrifugal type and may be driven by an electric motor or a steam turbine. The compressor is provided with both a seal-oil and lube-oil circuit and an automatic shutdown system to protect the machine against damage. The stripper column is used to remove light by-products from the product separator liquid. The stripper column usually contains 40 trays and incorporates a thermosiphon reboiler. Heat is usually supplied by the overhead vapor from the xylene column located upstream of the Parex unit. The stripper column is constructed of carbon steel. The combined feed exchanger is constructed of 1.25% Cr-0.5% Mo. Other heat exchangers are constructed of carbon steel.

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UOP TATORAY PROCESS 2.62 TABLE 2.7.1 Contaminant Nonaromatics Water Olefins Total chloride Total nitrogen Total sulfur
*Bromine index BASE AROMATICS PRODUCTION PROCESSES

Tatoray Feedstock Specifications Effect Increased cracking, increased H2 consumption, lower benzene purity Depresses transalkylation activity; reversible Promotes deposition of coke on catalyst Promotes cracking of aromatic rings; reversible Neutralizes active catalyst sites; irreversible Affects quality of the benzene product Limit 2 wt % max. 50 ppm max. 20 BI* max. 1 ppm max. 0.1 ppm max. 1 ppm max.

TABLE 2.7.2 Consumption*

Investment Cost and Utility 14.2 780 11 255 1.6

Estimated erected cost million $ U.S. Utility consumption: Electric power, kW High-pressure steam, MT/h Cooling water, m3/h Fuel fired, million kcal/h

*Basis: 98.5 ton/h (7800 BPD) of feedstock. Feed composition: 60 wt % toluene, 40 wt % C9 aromatics. Note: MT/h metric tons per hour.

CASE STUDY
A summary of the investment cost and utility consumption for a typical Tatoray unit is shown in Table 2.7.2. The basis for this case is a Tatoray unit processing 98.5 MT/h (7,800 BPD) of a feed consisting of 60 wt % toluene and 40 wt % A9. This case corresponds to the case study for an integrated UOP aromatics complex presented in Chap. 2.1. The investment cost is limited to the Tatoray unit and stripper column and does not include further downstream product fractionation. The estimated erected cost for the Tatoray unit assumes construction on a U.S. Gulf Coast site in 2002. The scope of the estimate includes engineering, procurement, and erection of equipment on the site.

COMMERCIAL EXPERIENCE
UOP has a long tradition of strong commitment to the BTX industry. Since the 1950s, more than 650 aromatics processing units have been licensed for BTX production, including process technologies for over 15 million MTA of PX production. As a result of this dedication, UOP has pioneered in all major technology advancements. Employing an integrated approach, UOP has focused on improving the economics of aromatics processing. This includes the substantial improvement of yields in the Platformer unit and the efficient conversion and separation of the aromatic rings in the downstream process units that produce the pure BTX products. Since October 2000, the total TA-5 catalyst installed capacity has reached 120,000 BPSD. Every TA-5 installation is operating well and meeting expectations with excep-

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tionally high selectivities to xylenes and benzene. Design feed rates range from 2600 to 65,000 BPSD. The market acceptance has been outstanding, making TA-5 catalyst one of the most successful products of its kind.

CONCLUSIONS
The transalkylation process plays a key role in the production of xylenes. Improvements in the Tatoray catalysts have substantially increased the aromatics complex performance and profitability. The new TA-5 catalyst is now rapidly gaining acceptance in the BTX industry since its introduction in late 2000. TA-5 catalyst offers the convenience of a dropin reload, twice the stability, and the same high conversion and selectivity to benzene and C8 aromatics as TA-4 catalyst.

REFERENCES
1. J. R. Mowry, UOP Aromatics Transalkylation Tatoray Process, chapter 5.6, in R. A. Meyers, ed., Handbook of Petroleum Refining Processes, 1st ed., McGraw-Hill, New York, 1986. 2. N. Y. Chen, Stud. Surf. Sci.Catal., vol. 38, p. 153, 1988. 3. A. Negiz, T. J. Stoodt, C. H. Tan, and J. Noe: UOPs New Tatoray Catalyst (TA-5) for Maximum Yields and Product Quality, AIChE Spring Conference, Fuels and Petrochemicals Division, New Orleans, La., March 2002. 4. J. J. Jeanneret, C. D. Low, and V. Zukauskas, New Strategies Maximize para-Xylene Production, Hydrocarbon Processing, vol. 6, p. 43, 1994. 5. J. H. DAuria and T. J. Stoodt, Harts Fuel Technology and Management, vol. 35, 1997.

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UOP TATORAY PROCESS

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