Hydrodealkylation

This is designed to produce benzene from toluene, whose upending from the chemicai standpoint is often difficult, and possibly from heavier aromatics available in surpluses, or sometimes from complete cuts. 

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Mobil s High Temperature Isomerization (MHTI) process, which was introduced in 1981, uses Pt on an acidic ZSM-5 zeoHte catalyst to isomerize the xylenes and hydrodealkylate EB to benzene and ethane (126). This process is particularly suited for unextracted feeds containing Cg aHphatics, because this catalyst is capable of cracking them to light paraffins. Reaction occurs in the vapor phase to produce a PX concentration slightly higher than equiHbrium, ie, 102—104% of equiHbrium. EB conversion is about 40—65%, with xylene losses of about 2%. Reaction conditions ate temperature of 427—460°C, pressure of 1480—1825 kPa, WHSV of 10—12, and a H2/hydtocatbon molar ratio of 1.5—2 1. Compared to the MVPI process, the MHTI process has lower xylene losses and lower formation of heavy aromatics. 

Benzene, toluene, and a mixed xylene stream are subsequently recovered by extractive distillation using a solvent. Recovery ofA-xylene from a mixed xylene stream requires a further process step of either crystallization and filtration or adsorption on molecular sieves. o-Xylene can be recovered from the raffinate by fractionation. In A" xylene production it is common to isomerize the / -xylene in order to maximize the production of A xylene and o-xylene. Additional benzene is commonly produced by the hydrodealkylation of toluene to benzene to balance supply and demand. Less common is the hydrodealkylation of xylenes to produce benzene and the disproportionation of toluene to produce xylenes and benzene. 

Properties. Table 4 contains typical gasoline quaUty data from the New Zealand plant (67). MTG gasoline typically contains 60 vol % saturates, ie, paraffins and naphthenes 10 vol % olefins and 30 vol % aromatics. Sulfur and nitrogen levels in the gasoline are virtually lul. The MTG process produces ca 3—7 wt % durene [95-93-2] (1,2,4,5-tetra-methylbenzene) but the level is reduced to ca 2 wt % in the finished gasoline product by hydrodealkylation of the durene in a separate catalytic reactor. 

Hydrogenolysis is analogous to hydrolysis and ammonolysis, which involve the cleavage of a bond induced by the action of water and ammonia, respectively. Chemical bonds that are broken by hydrogenolysis reactions include carbon—carbon, carbon—oxygen, carbon—sulfur, and carbon—nitrogen bonds. An example of hydrogenolysis is the hydrodealkylation of toluene to form benzene and methane ... 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

The benzene—toluene fraction is further fractionated in a small column, not shown in Figure 5, to recover benzene for recycle to the alkylation unit and toluene for sale. This toluene can be converted to benzene by hydrodealkylation but the high selectivity catalyst has reduced the formation of toluene in the dehydrogenation reactor to the point where the cost of installing a hydrodealkylation unit is difficult to justify even in a large styrene plant. 

Table 9 is a summary of world toluene supply and demand for 1996. North America, Asia, and Western Europe dominated the world s toluene business ia 1996. The three regions together accounted for over 85% of world production, imports, exports, and actual consumption, respectively. North America led ia production and consumption, while Asia led ia imports and exports. Table 10 presents the world toluene supply and demand. The worldwide demand for toluene increased by 7% from 1993 to 1994 and from 1994 to 1995, consecutively, because of higher hydrodealkylation (HDA) and disproportionation (TDP) operations, plus strong demand for all other derivatives. Over 70% of toluene is derived from a single source, catalytic reformate. 

The feedstock is usually extracted toluene, but some reformers are operated under sufftciendy severe conditions or with selected feedstocks to provide toluene pure enough to be fed directiy to the dealkylation unit without extraction. In addition to toluene, xylenes can also be fed to a dealkylation unit to produce benzene. Table 20 Hsts the producers and their capacities for manufacture of benzene by hydrodealkylation of toluene. Additional information on hydrodealkylation is available in References 50 and 52. 

Table 20. U.S. Producers of Benzene by Hydrodealkylation of Toluene and Their Annual Capacities ...

Toluene Hydrodeall lation. Benzene is produced from the hydrodemethylation of toluene under catalytic or thermal conditions. The main catalytic hydrodealkylation processes are Hydeal (UOP) and DETOL (Houdry) (49). Two widely used thermal processes are HD A (Arco and Hydrocarbon Research Institute) and THD (Gulf). These processes contribute 25—30% of the world s total benzene supply. 

In catalytic toluene hydrodealkylation, toluene is mixed with a hydrogen stream and passed through a vessel packed with a catalyst, usually supported chromium or molybdenum oxides, platinum or platinum oxides, on siHca or alumina (50). The operating temperatures range from 500—595°C... 

A typical catalytic hydrodealkylation scheme is shown ia Figure 3 (49). The most common feedstock is toluene, but xylenes can also be used. Recent studies have demonstrated that and heavier monoaromatics produce benzene ia a conventional hydrodealkylation unit ia yields comparable to that of toluene (51). The use of feeds containing up to 100% of C —aromatics iacreases the flexibiUty of the hydrodealkylation procedure which is sensitive to the price differential of benzene and toluene. When toluene is ia demand, benzene suppHes can be maintained from dealkylation of heavy feedstocks. 

Transall lation. Two molecules of toluene are converted iato one molecule of benzene and one molecule of mixed xylene isomers ia a sequence called transalkylation or disproportionation. Economic feasibiUty of the process strongly depends on the relative prices of benzene, toluene, and xylene. Operation of a transalkylation unit is practical only when there is an excess of toluene and a strong demand for benzene. In recent years, xylene and benzene prices have generally been higher than toluene prices so transalkylation is presendy an attractive alternative to hydrodealkylation (see also Btx... 

Miscellaneous Sources of Benzene. Benzene has been recovered from coal tar. The lowest boiling fraction is extracted with caustic soda to remove tar acids. The base washed oil is then distiUed and further purified by hydrodealkylation. 

The main producers of benzene in Canada are the Nova Corp. of Alberta, Petro-Canada, Inc., and Shell Canada Ltd. These three companies have an armual capacity of 567,000 t. Most Canadian benzene is obtained from catalytic reformate, pyrolysis gasoline, and hydrodealkylation. Coal is not an important source of benzene in Canada. 

Some of the principal Japanese producers of benzene are Mitsubishi Petrochemical Co., Ltd., Nippon Steel Chemical Co., Ltd., Sanyo Petrochemical Ltd., and Idemitsu Kosan Ltd. Until 1967, the main source of Japanese benzene was coal-based. Today, approximately 40—45% of benzene production in Japan is based on pyrolysis gasoline (74), about 40% catalytic reformate, and the remainder coke oven light oil and thermal hydrodealkylation. 

Biphenyl has been produced commercially in the United States since 1926, mainly by The Dow Chemical Co., Monsanto Co., and Sun Oil Co. Currently, Dow, Monsanto, and Koch Chemical Co. are the principal biphenyl producers, with lesser amounts coming from Sybron Corp. and Chemol, Inc. With the exception of Monsanto, the above suppHers recover biphenyl from high boiler fractions that accompany the hydrodealkylation of toluene [108-88-3] to benzene (6). Hydrodealkylation of alkylbenzenes, usually toluene, C Hg, is an important source of benzene, C H, in the United States. Numerous hydrodealkylation (HDA) processes have been developed. Most have the common feature that toluene or other alkylbenzene plus hydrogen is passed under pressure through a tubular reactor at high temperature (34). Methane and benzene are the principal products formed. Dealkylation conditions are sufficiently severe to cause some dehydrocondensation of benzene and toluene molecules. 

Rehable estimates of annual production of biphenyl in the United States are difficult to obtain. The 1990 figure is probably on the order of 16 million kg/yr of which about half is derived from hydrodealkylation sources. About 10% of the biphenyl derived from HD A sources is consumed, as 93—95% grade, in textile dye carrier appHcations. The remainder is used for alkylation or upgraded to >99.9% grades for heat-transfer purposes. Essentially all of the high purity biphenyl produced by dehydrocondensation of ben2ene is used as alkylation feedstock or is utili2ed directly in heat-transfer appHcations. 

The principal chemical uses of BTX are illustrated in Figure 1 and Hsted in Table 1 (2). A very wide range of consumer products from solvents to fibers, films, and plastics are based on BTX. The consumption of BTX is approximately in the proportions of 67 5 28, respectively. However, no BTX process gives BTX in these proportions. The economic value of benzene and xylenes (especially -xylene) is normally higher than that of toluene. Because of this, processes that convert toluene to benzene by hydrodealkylation (3) and disproportionate toluene to benzene and xylenes (4) have been commercialized. In addition, reforming processes that emphasize production of either benzene or -xylene [106 2-3] have been described (5). Since these are not classified as BTX processes they are not discussed in detail here. 

After the cmde BTX is formed, by reforming in this case, a heart cut is sent to extraction. Actually, the xylenes and heavier components are often sent to downstream processes without extraction. The toluene produced is converted to ben2ene, a more valuable petrochemical, by mnning it through a hydrodealkylation unit. This catalytic unit operates at 540—810°C with an excess of hydrogen. Another option is to disproportionate toluene or toluene plus aromatics to a mixture of ben2ene and xylenes using a process such as UOP s Tatoray or Mobil s Selective Toluene Disproportionation Process (STDP) (36). 

Toluene hydrodealkylation to benzene and methane Phthalic anhydride by air oxidation of naphthalene Trickle bed reactor for hydrodesulfurizatiou... 

Toluene is recovered as a high purity product by fractionating the mixed aromatics obtained from the extraction of catalytic reformate or powerformate. About 70 fractionation trays are required to produce toluene having a purity of 99.7 percent. Toluene is consumed principally as a feedstock for hydrodealkylation plants. Toluene is used in a number of solvent applications. 

Catalytic conversion processes include naphtha catalytic reforming, catalytic cracking, hydrocracking, hydrodealkylation, isomerization, alkylation, and polymerization. In these processes, one or more catalyst is used. A common factor among these processes is that most of the reactions are initiated hy an acid-type catalyst that promotes carhonium ion formation. 

Hydrodealkylation. Hydrodealkylation is a cracking reaction of an aromatic side chain in presence of hydrogen. Like hydrocracking, the... 

This process is designed to hydrodealkylate methylbenzenes, ethylbenzene and Cg aromatics to benzene. The petrochemical demand for benzene is greater than for toluene and xylenes. After separating benzene... 

The 1994 U.S. toluene production (of all grades) was approximately 6.8 billion pounds. Hydrodealkylating toluene to benzene was the largest end use in United States and West Europe, followed by solvent applications. 

Toluene is dealkylated to benzene over a hydrogenation-dehydrogenation catalyst such as nickel. The hydrodealkylation is essentially a hydrocracking reaction favored at higher temperatures and pressures. The reaction occurs at approximately 700°C and 40 atmospheres. A high benzene yield of about 96% or more can be achieved ... 

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