Ethylbenzene recovery

VS = vent gas scrubber EC = ethylbenzene recovery column DC = diethylbenzene recovery column. 

Figure 3 The effect of bag materials on ethylbenzene recovery (from SCHUETZLE et al. 1975 (8))...

The ethylbenzene recovery rate is usually over 95 per cent, and its purity greater than 99.8 per cent. The quality of the product obtained conditions that of its derivative, the styrene monomer, and its aptitude for polymeiizatioiL This depends on the presence of toluene or other aromatics in the feed, whose content must generally not exceed 0.3 per cent This fractionation can only be calculated conveniently on a computer. The theoretic cal number of trays is as high as 330 for 95 per cent recovery. Since the efiicieocy of these trays approaches 85 per Ccnu abotH 390 real trays must be used with reflux ratios up to 80 to 90. 

Styrene from ethylbenzene Reduced reaction temperature, elimination of ethylbenzene recovery 4,095 8.13 0.033... 

The Ebex process for ethylbenzene recovery was developed more recently and, although pilot scale operation has been demonstrated, no full-scale commercial unit has yet been built. ... 

Sales demand for acetophenone is largely satisfied through distikative by-product recovery from residues produced in the Hock process for phenol (qv) manufacture. Acetophenone is produced in the Hock process by decomposition of cumene hydroperoxide. A more selective synthesis of acetophenone, by cleavage of cumene hydroperoxide over a cupric catalyst, has been patented (341). Acetophenone can also be produced by oxidizing the methylphenylcarbinol intermediate which is formed in styrene (qv) production processes using ethylbenzene oxidation, such as the ARCO and Halcon process and older technologies (342,343). 

MPa (15—20 atm), 300—400 kg benzene per kg catalyst per h, and a benzene ethylene feed ratio of about 30. ZSM-5 inhibits formation of polyalkjlated benzenes produced with nonshape-selective catalysts. With both ethylene sources, raw material efficiency exceeds 99%, and heat recovery efficiency is high (see Xylenes and ethylbenzene). 

Eig. 4. Mobil—Badger process for ethylbenzene production H = heater Rx = reactor P = prefractionator BC = benzene recovery column ... 

The dehydrogenation of the mixture of m- and -ethyltoluenes is similar to that of ethylbenzene, but more dilution steam is required to prevent rapid coking on the catalyst. The recovery and purification of vinyltoluene monomer is considerably more difficult than for styrene owing to the high boiling point and high rate of thermal polymerization of the former and the complexity of the reactor effluent, which contains a large number of by-products. Pressures as low as 2.7 kPa (20 mm Hg) are used to keep distillation temperatures low even in the presence of polymerization inhibitor. The finished vinyltoluene monomer typically has an assay of 99.6%. 

In recent years alkylations have been accompHshed with acidic zeoHte catalysts, most nobably ZSM-5. A ZSM-5 ethylbenzene process was commercialized joiatiy by Mobil Co. and Badger America ia 1976 (24). The vapor-phase reaction occurs at temperatures above 370°C over a fixed bed of catalyst at 1.4—2.8 MPa (200—400 psi) with high ethylene space velocities. A typical molar ethylene to benzene ratio is about 1—1.2. The conversion to ethylbenzene is quantitative. The principal advantages of zeoHte-based routes are easy recovery of products, elimination of corrosive or environmentally unacceptable by-products, high product yields and selectivities, and high process heat recovery (25,26). 

Figure 10-2. The Badger process for producing ethylbenzene (1) reactor, (2) fractionator (for recovery of unreacted benzene), (3) EB fractionator, (4) polyethylbenzene recovery column.

A column is to be designed to separate a mixture of ethylbenzene and styrene. The feed will contain 0.5 mol fraction styrene, and a styrene purity of 99.5 per cent is required, with a recovery of 85 per cent. Estimate the number of equilibrium stages required at a reflux ratio of 8. Maximum column bottom pressure 0.20 bar. 

The second column in the distillation train of an aromatics plant is required to split toluene and ethylbenzene. The recovery of toluene in the overheads must be 95%, and 90% of the ethylbenzene must be recovered in the bottoms. In addition to toluene and ethylbenzene, the feed also contains benzene and xylene. The feed enters the column under saturated conditions at a temperature of 170°C, with component flowrates given in Table 9.10. Estimate the mass balance around the column using the Fenske Equation. Assume that the K-values can be correlated by Equation 9.68 with constants A , 5 and C, given in Table 9.10. 

Poro-xylene is an industrially important petrochemical. It is the precursor chemical for polyester and polyethylene terephthalate. It usually is found in mixtures containing all three isomers of xylene (ortho-, meta-, para-) as well as ethylbenzene. The isomers are very difficult to separate from each other by conventional distillation because the boiling points are very close. Certain zeoHtes or mol sieves can be used to preferentially adsorb one isomer from a mixture. Suitable desorbents exist which have boiling points much higher or lower than the xylene and displace the adsorbed species. The boihng point difference then allows easy recovery of the xylene isomer from the desorbent by distillation. Because of the basic electronic structure of the benzene ring, adsorptive separations can be used to separate the isomers of famihes of substituted aromatics as weU as substituted naphthalenes. 

According to the vendor. Microbial Fence has been used to treat groundwater contaminated with polycyclic aromatic hydrocarbons (PAHs) benzene, toluene, ethylbenzene, and xylenes (BTEX) and volatile organic hydrocarbons (VOCs) at petroleum, chemical, and wood treating facilities and manufactured gas plants. Microbial Fence was used alone or in conjunction with soil venting/bioventing, aquifer aeration, pump-and-treat methods, and/or recovery of non-aqueous-phase liquids (NAPLs). 

This technology has been used to treat polychlorinated biphenyls (PCBs), halogenated and nonhalogenated solvents, semivolatile organic compounds (SVOCs), polynuclear aromatic hydrocarbons (PAHs), pesticides, herbicides, fuel oils, benzene, toluene, ethylbenzene, and xylenes (BTEX), and mercury. This system has also treated Resource Conservation and Recovery Act (RCRA) hazardous wastes such as petroleum refinery wastes and multisource leachate treatment residues to meet RCRA Land Disposal Restrictions (LDR) treatment standards. 

When Wistar rats were exposed to 50, 300 or 600 ppm [0.22, 1.30 and 2.60 g/m ] ethylbenzene intermittently for up to 16 weeks, the urinary recovery of metabolites increased with dose but not linearly. The metabolic pattern of ethylbenzene was affected by exposure level but not by the duration of administration. The amounts of 1-phenylethanol and -hydroxyacetophenone increased with increasing exposure, but those of phenylglyoxylic acid and hippuric acid decreased (Engstrdm et al, 1985). 

The feed to an aromatics complex is normally a C6+ aromatic naphtha from a catalytic reformer. The feed is split into Cg+ for xylene recovery and C7 for solvent extraction. The extraction unit recovers pure benzene as a product and C7+ aromatics for recycling. A by-product of extraction is a non-aromatic C6+ raffinate stream. The complex contains a catalytic process for disproportionation and transalkylation of toluene and C9+ aromatics, and a catalytic process for isomerization of C8 aromatics. Zeolitic catalysts are used in these processes, and catalyst selectivity is a major performance factor for minimizing ring loss and formation of light and heavy ends. The choice of isomerization catalyst is dependent on whether it is desired to isomerize ethylbenzene plus xylenes to equilibrium or to dealkylate ethylbenzene to benzene while isomerizing the xylenes. Para-selectivity may also be a desired... 

EBMax is a liquid phase ethylbenzene process that uses Mobil s proprietary MCM-22 zeolite as the catalyst. This process was first commercialized at the Chiba Styrene Monomer Co. in Chiba, Japan in 1995 (16-18). The MCM-22-based catalyst is very stable. Cycle lengths in excess of three years have been achieved commercially. The MCM-22 zeolite catalyst is more monoalkylate selective than large pore zeolites including zeolites beta and Y. This allows the process to use low feed ratios of benzene to ethylene. Typical benzene to ethylene ratios are in the range of 3 to 5. The lower benzene to ethylene ratios reduce the benzene circulation rate which, in turn, improves the efficiency and reduces the throughput of the benzene recovery column. Because the process operates with a reduced benzene circulation rate, plant capacity can be improved without adding distillation capacity. This is an important consideration, since distillation column capacity is a bottleneck in most ethylbenzene process units. The EBMax process operates at low temperatures, and therefore the level of xylenes in the ethylbenzene product is very low, typically less than 10 ppm. 

The monoalkylation selectivity of the alkylation step refers to the fraction of ethylene that reacts to form ethylbenzene, as opposed to forming polyethylated species. To suppress the formation of PEBs, benzene must be fed to the alkylation reactor in considerable excess (frequently five to seven times the stoichiometric requirement). Equipment in the alkylation reaction and benzene recovery systems must therefore be sized to accommodate the flow of excess benzene, and energy must be expended to recover the excess benzene from the reactor effluent. However, the superior monoalkylation selectivity and stability of MCM-22 permits operation with reduced benzene feed rates - in the range of two to four times the stoichiometric requirement - without excessive PEB formation (see Table 11.1). 

EPA 1989d. National Emission Standards for Hazardous Air Pollutants Benzene Emissions from Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke By-Products Recovery Plants. U.S. Environmental Protection Agency. 54 FR 38044. 

Application The Isomar process isomerizes C8 aromatics to mixed xylenes, to maximize the recovery of paraxylene in a UOP aromatics complex. Depending on the type of catalyst used, ethylbenzene (EB) is also converted into xylenes or benzene. 

The main drawbacks of the non-oxidative dehydrogenation reaction can be summarized as, the thermodynamic limitation, the low conversion rate, the need for recovery of unreacted ethylbenzene, the high energy consumption, and deactivation of the catalyst. Thus in recent years several alternatives to overcome those problems have been investigated. 

Although not yet industrialized, the recovery of ethylbenzene contained in these cuts by sdective adsorption is also planned, particidarly by Exxon and UOP (Universal Oil Products). In Exxon s process, e desired hydrocarbon is preferentially adsorbed, while UOP s Ebex process is similar in prindple to the Sorbex type of technique, in whief the ethylbenzene remains in the raffinate. Asahi also has developments under way ii this area. 

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