6.

BTX Aromatics ChE EL 3: Introduction to Petrochemical Engineering

Uses of BTX (Butene-Toluene-Xylene). Source: Chemical Process and Design Handbook by James G. Speight (2002)

BTX (benzene-toluene-xylene) are naturally occurring compounds in crude oil but are at low
concentrations. In a petroleum refinery, BTX are primarily produced through catalytic reforming which
increases the concentration of BTX which makes it more economical to separate. The BTX fraction from
the catalytic reforming stream (or reformate) is separated from the other HC’s through extractive
distillation. The BTX fraction is then fractionated to its pure components.

BTX are also obtained from pyrolysis gasoline, a byproduct of naphtha crackers. Pyrolysis gasoline may
contain up to about 65 percent aromatics, and about half of which is benzene. Likewise, the aromatics are
separated from other HC’s through extractive distillation.

On-purpose benzene is manufactured by toluene hydrodealkylation. Transalkylation of toluene also

produces benzene along with mixed xylene aside from benzene. BTX had also been extracted from coal
tar but this has been supplanted by the above processes.

The figure above shows the primary uses of BTX aromatics.

Benzene (C6H6, boiling point: 80°C, density: 0.8789, flash point: −11°C, ignition temperature: 538°C), is a
volatile, colorless, and flammable liquid aromatic hydrocarbon possessing a distinct, characteristic odor.
Benzene is practically insoluble in water (0.07 part in 100 parts at 22°C); and fully miscible with alcohol,
ether, and numerous organic liquids.

Toluene (C6H 5CH 3, boiling point: 110.8°C, density: 0.8548, flash point: 4.4°C, ignition temperature:
552°C) is a colorless, flammable liquid with a benzene-like odor that is essentially insoluble in water but is
fully miscible with alcohol, ether, chloroform, and many other organic liquids. Toluene dissolves iodine,
sulfur, oils, fats, resins, and phosgene. When ignited, toluene burns with a smoky flame. Unlike benzene,

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toluene cannot be easily purified by crystallization. About one-half of toluene consumption is for the
production of benzene. The production of diisocyanates from toluene is increasing.

The properties of xylenes will be discussed in a later part of this document.

CATALYTIC REFORMING, SOLVENT EXTRACTION OF BTX

Catalytic reforming is a petroleum refining operation for the production of high octane gasoline. The feed
to catalytic reforming is straight-run naphtha which underwent hydrotreating to remove catalyst poison
such as sulfur, oxygen and nitrogen compounds and also to remove olefins. The reformer uses noble metal
such as platinum-rhenium on a catalyst support.

Benzene manufacture by the platforming process.

The product, reformate , is rich in aromatics and excess hydrogen. It is sent to a separator where the light
hydrocarbons are removed, then to a debutanizer. The debutanized reformate is sent to a splitter where
the BTX fractions and other nonaromatic HC’s are produced overhead and the heavier products, C8’s and
C9’s, are removed from the bottom.

Since the aromatics form an azeotropic mixture with other hydrocarbons, they are usually separated
through solvent extraction. Examples of solvents that are used in this process include tetramethylene
sulfone, diethylene glycol, N-methylpyrrolidinone process, dimethylformamide, liquid sulfur dioxide, and
tetraethylene glycol. In solvent extraction, the solvent is passed countercurrently against the mixed
hydrocarbon feed. A mixture of aromatic and paraffinic hydrocarbons serves as reflux.

After solvent extraction, the BTX fraction is separated from the solvent and to its individual components
through distillation columns.

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Schematic of extractive distillation.

HYDRODEMETHYLATION OF TOLUENE

One method of increasing the production of benzene is by the hydrodemethylation of toluene. This
reaction may be either catalytic or through thermal conditions.

Benzene manufacture by toluene hydrodealkylation

The chemical reaction In the catalytic hydrodealkylation of toluene is as follows:

Toluene, obtained from extractive distillation, is mixed with a hydrogen. This stream is passed through a
packed catalyst (usually supported chromium or molybdenum oxides, platinum or platinum oxides, on silica
or alumina) bed reactor at operating temperatures of 500 to 595°C and pressures are usually 4 to 6 MPa.
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The reaction is exothermic and temperature control (by injection of quench hydrogen) is necessary at
several places along the reaction sequence. Conversions per pass typically reach 90 percent and
selectivity to benzene is often greater than 95 percent. The catalytic process occurs at lower
temperatures and offers higher selectivity but requires frequent regeneration of the catalyst. Products
leaving the reactor pass through a separator where unreacted hydrogen is removed and recycled to the
feed. Further fractionation separates methane from the benzene product.

TRANSALKYLATION OF TOLUENE

Benzene and mixed xylenes are also produced by the transalkylation of toluene in which two molecules of
toluene are converted into one molecule of benzene and one molecule of mixed xylene isomers. Although
the mixed xylenes from toluene disproportionation are generally more costly to produce than those from
catalytic reformate or pyrolysis gasoline, their principal advantage is that they are very pure and contain
essentially no ethylbenzene.

In the process, toluene and C9 aromatics are mixed with liquid recycle and recycle hydrogen, heated to
350 to 530°C at 150 to 737 psi (1 to 5 MPa), and charged to a reactor containing a fixed bed of noble
metal or rare earth catalyst with hydrogen-to-feedstock mole ratios of 5:1 to 12:1. Following removal of
gases, the separator liquid is freed of light ends and the bottoms are then clay treated and fractionated to
produce high-purity benzene and xylenes. The yield of benzene and xylene obtained from this procedure is
about 92 percent of the theoretical.

Benzene manufacture by the transalkylation of toluene.

The chemical reaction is as follows:

Toluene diisocyanate is made into flexible foam polyurethanes for cushioning in furniture, automobiles,
carpets, bedding, polyurethane coatings, rigid foams, and elastomer.

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XYLENES

The general term xylenes refers to the C8 aromatic isomers (CH3C6H4CH3) with the methyl groups in
positions ortho, meta, and para to each other. Thus, the xylenes consist of three isomers: o-xylene, m-
xylene, and p-xylene

The xylenes are colorless, flammable liquids with properties that are significantly different from each other
or significantly similar to each other, depending upon the perspective and the need for separation of the
isomers.

Melting Point, °C Boiling Point, °C Density, g/mL

o-xylene −25°C 144.0 0.8968

m-xylene −47.4°C 139.1 0.8684

p-xylene 13.2°C 138.5 0.8611

As was mentioned in previous discussion, xylenes are produced from catalytic reforming or steam
reforming of naphtha as well as in toluene disproportionation. The mixed xylenes stream is then processed
further to produce high-purity p-xylene and/or o-xylene. Because of the close boiling points of p-xylene
and m-xylene, production of high-purity p-xylene by distillation is impractical and methods such as
crystallization and adsorption are used.

In the separation of the xylenes, the C8 mixture is cooled to −70°C in the heat exchanger refrigerated by
ethylene. Because of the difference in melting points (o-xylene −25.0°C; m-xylene – 47.9°C; p-xylene
13.2°C), the para-isomer crystallizes preferentially. The other two isomers remain liquid as a mixture and
the solid para-isomer is centrifuged and separated. A second cooling cycle needs only propane as
coolant, and complete separation is accomplished with an optional third cooling cycle.

Because of the large demand for p-xylene, another method is now being used to increase the percentage
of the para-isomer in mixed xylenes. They are heated at 300°C with an acidic zeolite catalyst, which
equilibrates the three xylenes to an o, m, p ratio of 10:72:18. The para-isomer is separated by fractional
crystallization, whereas the ortho-meta mixture is reisomerized with the catalyst to produce more para-
isomer.

To prevent the buildup of ethylbenzene in the recycle loop, the catalysts are also designed to convert
ethylbenzene to either benzene and xylenes or to benzene and diethylbenzene.

The xylenes can be used as a mixture or separated into pure isomers, depending on the application. P-
xylene is used in the manufacture of terephthalic acid, which is reacted with ethylene glycol to give poly
(ethylene terephthalate). Large amounts of this polyester are used in textile fibers, photographic film, and
soft drink bottles.

O-xylene is used in the manufacture of phthalic anhydride, an intermediate in the synthesis of plasticizers,
substances that make plastics more flexible. A common plasticizer is dioctyl phthalate.

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Manufacture of xylenes by catalytic reforming and toluene disproportionation.

REFERENCES:

James G. Speight. 2002. Chemical Process and Design Handbook. MANUFACTURE OF CHEMICALS,
Chapter. McGraw-Hill Professional, AccessEngineering.

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