Applied Catalysis A: General 181 (1999) 355±398 Disproportionation and transalkylation of alkylbenzenes over zeolite catalysts Tseng-Chang Tsaia, Shang-Bin Liub, Ikai Wangc,* aRe®ning and Manufacturing Research Center, Chinese Petroleum Corporation, Chiayi 600, Taiwan bInstitute of Atomic and Molecular Sciences, Academia Sinica, PO Box 23-166, Taipei 106, Taiwan cDepartment of Chemical Engineering, National Tsing-Hua University, Hsinchu 300, Taiwan Received 13 June 1998; received in revised form 3 October 1998; accepted 5 November 1998 Abstract Disproportionation and transalkylation are important processes for the interconversion of mono-, di-, and tri-alkylbenzenes. In this review, we discuss the recent advances in process technology with special focus on improvements of para-isomer selectivity and catalyst stability. Extensive patent search and discussion on technology development are presented. The key criteria for process development are identi®ed. The working principles of para-isomer selectivity improvements involve the reduction of diffusivity and the inactivation of external surface. In conjunction with the fundamental research, various practical modi®cation aspects particularly the pre-coking and the silica deposition techniques, are extensively reviewed. The impact of para-isomer selective technology on process economics and product recovery strategy is discussed. Furthermore, perspective trends in related research and development are provided. # 1999 Elsevier Science B.V. All rights reserved. Keywords: Disproportionation; Transalkylation; Alkylbenzenes; Zeolites; Diffusivity 1. Introduction Dialkylbenzenes, a subcategory of aromatics, include xylenes, diethylbenzene (DEB) and dipropyl- Aromatics have a wide variety of applications in the benzene (DPB), all of which may be derivable to petrochemical and chemical industries. They are an valuable performance chemicals. For example, important raw material for many intermediates of xylenes are the key raw materials for polyesters, commodity petrochemicals and valuable ®ne chemi- plasticizers and engineering plastics [3], p-DEBisa cals, such as monomers for polyesters, engineering high-valued desorbent used in p-xylene adsorptive plastics, intermediates for detergents, pharmaceuti- separation process [4], whereas increasing applica- cals, agricultural-products and explosives [1]. Among tions of diisopropylbenzene (DIPB) have been found, them, benzene, toluene and xylenes (BTX) are the ranging from photo-developers, antioxidants to engi- three basic materials for most intermediates of aro- neering plastics [5]. Process development in aromatic matic derivatives (Fig. 1) [2]. interconversion is therefore an important research task with great industrial demands. There are many driving forces for the development *Corresponding author. of a new process. In addition to the economically 0926-860X/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved. PII: S0926-860X(98)00396-2 356 T.-C. Tsai et al. / Applied Catalysis A: General 181 (1999) 355±398 Fig. 1. Derivatives of benzene, toluene and xylene; from refs. [1,2]. relevant variables such as market demand, feedstock processes. Solid acid catalysts have long been demon- availability and cost, and operating cost, legislative strated as the keys to the success of the historical aspects such as environmental laws, and new refor- efforts. Tanabe et al. [6] comprehensively discussed mulated gasoline speci®cations, etc., also come into acid catalyst properties in his well-known review in play. solid acids and bases. Aromatics alkylation was one In response to the worldwide environmental aware- typical example of the use of solid acid catalysts in the ness, there are active programs to search for clean development of environmentally sound processes. T.-C. Tsai et al. / Applied Catalysis A: General 181 (1999) 355±398 357 Zeolites were used to replace the traditional Friedel± Craft catalysts, making the process cleaner, less cor- rosive and more economic competitive. By using Friedel±Craft catalysts, solid and liquid wastes in ethylbenzene (EB) production of 390 000 tons/year were 500 and 800 tons/year, respectively. By using ZSM-5 catalyst, the wastes were signi®cantly reduced to 35 and 264 tons/year, respectively [7]. The 1990 Clean Air Act (CAA) had re-de®ned the gasoline speci®cations to enforce the so-called ``refor- Fig. 3. Worldwide BTX market growth curves. mulated gasoline'' (RFG) act [8]. The initial stage of the enforcement applied the Simple Model regulation, by which the maximum benzene content in gasoline is wide production capacity ratio for B:T:X obtained limited to less than 1 vol% [9,10]. In a later stage, a from the two above mentioned processes is Complex Model regulation will be applied, by which 32:36:32 [11], and varies with regional locations. This the maximum content of total aromatics is likely to be contrasts to their market demands in petrochemical limited to as low as 25 vol%. As a result, many industry (without accounting for the demand in gaso- international projects have been developed to modify line pool) of 55:11:34 [12±16]. In other words, toluene re®nery structures in order to meet the challenge. The which has the lowest market demand is always in modi®cations involved switching the application of surplus from the production of reformate and pyrolysis aromatics from gasoline to petrochemicals, especially gasoline, whereas benzene and xylenes are in strong to benzene and xylenes. The composition restrictions demand with the average annual growth rates of imposed on the ``reformulated gasoline'' therefore not around 10% [16±18], as shown in Fig. 3. As a result only have signi®cant impact on gasoline composition, of demand and supply, the price for toluene is always but also on the economics of aromatics production lower than the other aromatics. For example, the processes. historical BTX market price in Europe is presented The processes of catalytic reforming and naphtha in Fig. 4. The conversion of dispensable toluene into pyrolysis are the main sources of BTX production. the more valuable aromatics therefore has an eco- The product yields of those processes are normally nomic incentive. A serious discrepancy between pro- controlled by thermodynamics and hence result in a duction and market demand was also found for most substantial mismatch between the supply and the dialkylbenzene isomers, among which the para-iso- actual market demands. As shown in Fig. 2, the world- mer apparently has the greatest market demand. In response to market situation and legislation changes, the main areas of new aromatics process innovations were: 1. conversion of surplus toluene, Fig. 2. Comparison of worldwide BTX distribution patterns of production and market demand. Fig. 4. Historical BTX price in Europe market. 358 T.-C. Tsai et al. / Applied Catalysis A: General 181 (1999) 355±398 2. upgrading of heavy aromatics, which are benzene ing et al. [21] on the Mobil's aromatics processes, and xylene (B & X) oriented, Haag et al. [22] on acid catalytic aspects of medium- 3. selective production of para-dialkylbenzene iso- pore zeolites, and recently, Chen et al. [23] on indus- mer against thermodynamic equilibrium, such as trial shape selective catalysis, Venuto et al. [24] on p-xylene and p-DEB, and microporous catalysis chemistry, Ribeiro et al. [25] on 4. production of dialkylbenzenes with carbon number techniques of zeolite modi®cation, Khouw and Davis of alkyl group larger than 3. [26] particularly on metal encapsulation and in the application of electro- and photo-chemical reactions. Improving and ®nding cost effective disproportio- nation and transalkylation catalytic processes are interesting and challenging tasks in industrial research. In recent years, there have been many research attempts in the area of process development. These new processes not only have had a great impact on process economics, such as production cost and supply and demand of aromatics, but also on the optimum process integration between conversion and separation units in a traditional dialkylbenzene production complex. Several newly developed novel processes produced dialkylbenzenes which are particularly rich in para- isomers compared to their thermodynamic equili- brium compositions, for example, MSTDPSM, Disproportionation and transalkylation are the two MTPXSM and PX-PlusSM for p-xylene production major practical processes for the interconversion of [27±30] and TSMC's (Taiwan Styrene Monomer) aromatics, especially for the production of dialkyl- selective PDEB process for p-DEB production [31]. benzenes. The generic formulas for the two processes In addition, several new emerging heavy aromatics are given in reactions (1) and (2), respectively. They conversion processes with maximum approach to are coined as ``alkyl group transfer reactions'', which thermodynamic equilibrium xylene yield have also deal mainly with the alkyl group transfer among been developed, namely TatoraySM [32±34] and different aromatic rings. Such processes are com- TransPlusSM [35±38]. monly used in the conversion of toluene into benzene The present review is presented from the perspec- and xylenes. Moreover, disproportionation of EB and tive of process technology of aromatic interconversion isopropylbenzene (IPB) yields diethylbenzene (DEB) along with fundamental research on shape selective and dipropylbenzene (DPB), respectively. catalysis. In particular, the selection of a suitable Owing to the recent development in catalytic chem- zeolite