Hydrodealkylation unit

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. 

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. 

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). 

The feedstock in hydrodealkylation units is heated to 1,200° F (650°C) in a preheat furnace before entering the reactor. Above 1,100°F (590°C), metal dusting or catastrophic carburization occurs on ail alloys that are otherwise suitable for the temperature conditions. The attack is very rapid and takes the form of round bottom pits. The surface of the remaining metal is heavily carburized. A small quantity of sulfur (0.05 to 0.5 wt%) in the form of hydrogen sulfide or mercaptan added to the feed will prevent attack. Aluminizing has also been used to prevent attack. 

EB-poor C8 aromatics cuts are produced which favors further pX separation Low-value toluene and C9+ aromatics (that are generally sent to the gasoline pool because of their high octane number) are transformed into high value pX Toluene hydrodealkylation units can be easily revamped into TDP or transalkylation units... 

Revamp of a toluene hydrodealkylation process. This prob-lan considers some waste-minimization concepts. Our operating toluene hydrodealkylation unit, shown in Figure 5.13, involves the hydrogenation of toluene to benzene and methane. An equi-lihium side reaction produces a small quantity of biphenyl. To be more competitive, and eliminate waste, the process needs to be studied for a possible revamp. The customer for our small production of biphenyl has informed us that it will not renew its contract with us, and we have no other prospective buyer for biphenyl. Also, a membrane separator company believes that if we install their equipment, we can reduce our makeup hydrogen requirement. Make preliminary process design calculations with a simulator to compare the two alternatives below, and advise me of the technical feasibility of the second alternative and whether we should consider such a revamp further. For your studies, you will have to perform mainly material balance calculations. You will not make detailed distillation calculations, and liquid pumps need not be modeled. For the second alternative, calculate the required area in square feet of the membrane unit and determine if it is reasonable. 

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 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. 

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... 

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 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. 

These same notions can be extended to an entire plant in which several unit operations are connected together. The HDA process for hydrodealkylation of toluene to form benzene is a good example of where an eigenstructure can be found that provides a more easily and simply controlled plant. See Fig. 8.15. Assuming that the toluene feed rate to the unit is fixed, this plant has 22 valves that must be set. There are 11 inventory loops (levels and pressures), so they require 11 valves. One possible conventional control structure is shown in Fig. 8.15. 

Since toluene is nothing more than benzene with a methyl group attached, creating one from another is relatively easy. Benzene, toluene, and for that matter, xylenes too, are coproduced in the processes just described—coke making, cat reforming, and olefin plants operations. The ratio of benzene to the other aromatics production is rarely equal to the chemical feedstock requirements.. fo.r the three. One method for balancing supply and demand is toluene hydrodealkylation (HDA). This process accounts for 10—15% of the supply of benzene in the United States and is a good example of what can be done when one or more coproducts are produced in proportions out of balance with the marketplace. 

To the dismay of toluene lovers, if there are any, the volume growth of benzene has overshadowed that of toluene, and toluenes major use is to make benzene in hydrodealkylation and toluene disproportionation units. About 50% of the toluene recovered in the United States is used this way. Conversion to para-xylene is also of growing importance. 

The BT mixture can be easily separated by simple distillation in a two-column sequence, or in a single column with side stream. The last alternative is preferred because it is advantageous energetically. The side-stream toluene is usually sent to hydrodealkylation or transalkylation units to increase the yield in benzene and xylenes. The bottom product goes to higher aromatics treatment... 

Cg products coming from the reformer can be directly processed in a xylene isomerization unit, using a Pt ZSM-5 zeolite catalyst, and operating at high temperature. Under these conditions, the aliphatics are cracked to lighter products, and the ethylbenzene is hydrodealkylated to benzene and ethane (170,199). 

Laboratory data indicate that the reactions proceed irreversibly without a catalyst at temperatures in the range of 1,200-1,270°F with approximately 75 mol% of the toluene converted to benzene and approximately 2 mol% of the benzene produced in the hydrodealkylation reaction converted to biphenyl. Since the reactions occur in series in a single processing unit, just a single reaction operation is positioned in the flowsheet, as shown in Figure 4.16. The plant capacity is based on the conversion of 274.2 Ibmol/hr of toluene, or approximately 200 MMlb/yr, assuming operation 330 days per year. 

When steam cracking or naphtha reforming produce an aromatics mixture short in benzene or o- and p-xylene, some interconversion is practiced. Toluene can be hydrodealkylated to benzene. Xylene can be isomerized to increase yields of o- and p-xylene. The analysis for aromatics thus falls into two general types to meet two different needs. Analysis for process optimization assists in obtaining the maximum product at the minimum unit cost. This involves analysis of feeds, products, and raffinate (purge) streams. These analyses must be tailored to the process and the plant streams involved. Generally, it is desirable to have one analytical procedure to apply to a variety of sample types. The final product specification analysis can also be used for process control. The ASTM standard... 

Estimate the quantities and yearly costs of the appropriate utilities for the following pieces of equipment on the toluene hydrodealkylation PFD (Figure 1.5). It is assumed that the stream factor is 0.95 and that all the numbers on the PFD are on a stream time basis. The duty on all of the units can be found in Table 1.7. 

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