ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING
Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
Published online 21 August 2007 in Wiley InterScience
(www.interscience.wiley.com) DOI:10.1002/apj.018
Research Article
Benzene production and economics: a review
Joseph C. Gentry*
GTC Technology, Houston, TX 77077, USA
Received 6 June 2006
ABSTRACT: This paper reviews the fundamental aspects of benzene manufacturing, benzene use, and the economics
of benzene production plants. The objective is to provide an essential overview of the benzene industry that will assist
in improved business and technological decision-making.  2007 Curtin University of Technology and John Wiley &
Sons, Ltd.
KEYWORDS: benzene; BTX; Techtiv; extractive distillation
THE CORNERSTONE OF AROMATICS
In the early days of the chemical industry, Michael Fara-
day (in 1825) first isolated benzene from an oily film
that deposited on the gas lamps used for lighting. A few
years after its discovery, another chemist, found that he
could produce this compound by heating a chemical
that had been isolated from the gum benzoin. Hence
he called it benzin, which later became in the IUPAC
nomenclature, ‘benzene’. In 1865, the German chemist
August Kekulé, proposed its hexagonal ring structure
with alternating double bonds (Fig. 1). Since then ben-
zene has become one of the most-studied chemicals in
history, as scientists and engineers have discovered a
number of industrial uses for this ring-shaped molecule.
The benzene ring is a fundamental part of all aromat-
ics, others being toluene, xylenes, alkylbenzenes, etc.
Aromatics are so named because of their sweet smell.
GOOD PRODUCT–BAD PRESS
Benzene is a clear flammable liquid with a boiling point
of 80.1 ◦ C, within the range of naphtha. It is distinctive
in its chemical stability and lack of polarity. Prior to dis-
covery of the various derivatives, benzene was primarily
used in gasoline blending because of its octane value;
and as a solvent due to its high hydrocarbon solubility.
In today’s modern chemical processing industry, ben-
zene is more profitably used as a basic building block
for important chemical intermediates, including plastics,
fabrics, dyes, and detergents.
*Correspondence to: Joseph C. Gentry, GTC Technology, 1001
S. Dairy Ashford, Ste. 500, Houston, TX 77077, USA. Tel: (+1) 281
597 4800. E-mail: igentry@gtchouston.com
 2007 Curtin University of Technology and John Wiley & Sons, Ltd.
Benzene is among the most widely produced petro-
chemicals in the world. Current production is approx-
imately 37 million tons per year, while demand is
projected to grow annually at 3.8% (Source: CMAI).
Figure 2 shows the demand for benzene in the USA
(2004), based on use (Fig. 2).
While the demand growth has been respectable, the
supply has struggled to keep up for various reasons. The
result has been a sharp rise in benzene pricing. With few
alternatives for the myriad products that are made from
benzene, this has lead to premium pricing and is shaping
a new historical trend. As the availability, quality, and
uses of hydrocarbon fuels evolve over the next few
decades, chemical producers will continue to look at
various benzene production routes in order to satisfy
demand. The derivatives of benzene are found across
nearly the entire spectrum of industrial and consumer
goods.
• When benzene is alkylated, dehydrogenated, and
polymerized, the products include styrofoam cups
and automobile tires.
• When oxidized and polymerized, this cornerstone
aromatic can be processed into contact lenses and
compact disks.
• When reacted with nitric acid and subjected to
chemical rearrangement, benzene can be converted
into nylon fabric (Fig. 3).
Concerns have been raised in the chemical industry
regarding products that can cause physical illness, when
used improperly or due to severe when exposure. Many
refiners have responded to consumer pressures and now
avoid making, or have even begun destroying, the ben-
zene through hydrogenation. With the preponderance
of experience and safe operation by industrial produc-
ers, and considering the tremendously favorable process
Asia-Pacific Journal of Chemical Engineering BENZENE PRODUCTION AND ECONOMICS 273

Benzene will continue to play an important role

in the daily lives of people around the world, in
spite of the environmental concerns. The alternative
names of benzol, phenylene, or cyclohexatriene seem
to raise less criticism! The various regulations have
driven down the levels of benzene in our motor fuels,
and restricted the emissions from our chemical plants,
however, this molecule plays an important role as a
Figure 1. Benzene molecular structure.
building block for various common products. Benzene
production should be no more hazardous than any other
2004 US BENZENE DEMAND commodity petrochemical if due regard is paid to the
TOTAL DEMAND = 8955 KMTA recommendations of the safety standards.
Aniline
Alkyl Benzene
Aniline Chlorobenzene
Chlorobenzene HOW TO MAKE AND PURIFY BENZENE
Cumene
Cyclohexane
Cumene
Some benzene occurs naturally in fossil fuels, depend-
EB / SM
EB / SM ing upon the severity of the conditions of biomass
Alkyl Benzene decomposition. However, virtually all of the benzene
used for petrochemical applications is created through
Cyclohexane man-made hydrocarbon conversion processes. Benzene
emanates from these processes through the formation
Figure 2. Demand chart for benzene source, CMAI of the ring structure from other hydrocarbons. These
aromatics Supplement, Jan 21, 2005 Issue 977. This figure
is available in colour online at www.apjChemEng.com.
processes can be divided into two broad categories:
cracking and reforming.
Thermal-cracked or reformed benzene-containing
economics, these refiners may need to reconsider their streams cannot be used directly in the downstream
process configuration decisions. processes. Most of the downstream processes require

O + C=C O C C O C = C + H2

OOH

CH3CHCH3 CH3CCH3 OH
O
O2 H+
O + C3= O O O + CH3CCH3

O OH O O
H2 O2 HNO3
O + HO - C - (CH2)4 - C - OH

Figure 3. End-products produced using benzene. This figure is available in colour

online at www.apjChemEng.com.
 2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
DOI: 10.1002/apj
274 J. C. GENTRY Asia-Pacific Journal of Chemical Engineering

a high-purity benzene product (typically 99.9+ wt%).
Since other close-boiling (and azeotrope-forming) com-
ponents are also contained in the feed streams along
with the benzene, simple fractional distillation cannot
be utilized to produce high-purity product. Therefore,
other techniques such as solvent-based extractive pro-
cesses are required. The broad technology options are
reviewed below for the formation of the benzene ring,
and the purification techniques for high-purity benzene
production.
Formation of benzene ring
Cracking
In this operation, hydrocarbon molecules such as
naphtha or gasoil are thermally cracked into smaller
molecules at high temperatures. This leads to pro-
duction of a variety of lighter, unsaturated hydrocar-
bons including C1–C4 compounds (gaseous products),
and C5+ liquid products. The liquid product, typically
called pyrolysis gasoline or pygas for short, contains
a high percentage of benzene (around 40–45%) and
other aromatics. Thermal cracking of C2–C4 paraffins
also produce benzene due to ring condensation, but to
a much lesser extent.
The amount of pygas and the quantity of contained
aromatics depends upon the feedstock that is being
cracked (light vs heavy), and the severity of cracking
(high vs low). Typically, heavier feedstock and higher-
severity operations lead to production of more benzene
and aromatics. This is because the benzene ring struc-
ture is inherently very stable.
Benzene is also found in the coke oven light oil
stream (COLO) that is produced in a steel plant; this was
one of the earliest sources of commercially produced
benzene. Other processes such as hydrocracking and
fluid catalytic cracking also produce benzene, although
in quantities usually insufficient to justify recovery.
These types of catalytic processes are intentionally
designed to favor production of other types of hydro-
carbons (Fig. 4).
Reforming
In reforming, hydrocarbon molecules (typically in the
naphtha-range) are catalytically ‘reformed’ to produce
aromatics-rich C5+ liquid products. Although the pri-
mary use of reformed products is as motor fuels, ‘cat’
reforming also serves as a major source for benzene
and other aromatic compounds. A full-range reformate
contains between 5–15% benzene and 40–60% heavier
aromatics.
Technologies are also now available to reform other
feedstocks to produce benzene-rich products (e.g. LPG
and light naphtha), although these are generally not
economical with market-priced feedstocks (Fig. 5).
Ring rearrangement
As an extension to the above two methods, heavier
aromatics which are coproduced can be converted to
benzene through various methods. These include:
• Hydrodealkylation (HDA) (cracking the alkyl groups
from heavier aromatics to produce benzene). HDA
O + 3H2
C - C - C - C - C - C O + 4H2
Figure 5. Reforming chemistry.

H2
Primary Product
CH4
C2H4
C2H6
C3H6
C3H8 Important
C
C4H8 By-products
C4H10
C-C-C-C-C-C-C-C
C5
C6H6
C7
C8
.
.
.
.
fuel oil

Figure 4. Cracking chemistry.

 2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
is the only specific method of benzene primary
production.
• Transalkylation (combining toluene and C9+ aromat-
ics to produce benzene and xylenes through rear-
rangement of the alkyl groups).
• Disproportionation (shifting alkyl groups from
toluene to produce benzene and xylenes) (Fig. 6).
In most of these methods described above, benzene
is not a stand-alone product or the primary product of
interest.
For example, steam crackers are used to produce
ethylene and propylene; reformers are used to produce
high-octane gasoline blending material; and the ring-
arrangement processes are usually used to produce
xylenes for conversion to paraxylene. Since benzene
is considered a co-product, production volumes and
attendant economics are constantly varying.
Purification to high-purity benzene
As already indicated, benzene contained in the pygas,
reformate, COLO, or other hydrocarbons streams cannot
be used directly in the downstream processes. Solvent-
based extractive techniques which utilize the nonpolar
nature of benzene and its preferential solubility in
polar solvents, are required to separate the aromatics.
Since heavier aromatics such as toluene and xylenes
are coproduced with the benzene-containing streams,
it is sensible to purify the heavier aromatics along
with benzene. Two main processes are used for this
CH3
HDA O +
CH3
Transalkylation O +
CH3
CH3
Disproportionation
O +
C2H5
EB-Dealkylation O +
(PX manufacture)
Figure 6. Ring rearrangement chemistry.
 2007 Curtin University of Technology and John Wiley & Sons, Ltd.
BENZENE PRODUCTION AND ECONOMICS 275
purpose: liquid–liquid extraction (LLE) and extractive
distillation (ED) (Fig. 7).
Traditionally, refinery operators have relied on LLE
technologies for aromatics recovery. This is because the
older versions of ED could not produce good perfor-
mance of product recovery and purity across multiple
carbon numbers. The first and second generation of ED
solvents were not selective enough to cleanly separate
more than one aromatic species at a time, and were
plagued by poor performance due to 3-phase distilla-
tion. Some of the processes used nitrogen-based sol-
vents which are permanent poisons in many benzene
consuming units. This is no longer an issue with the
introduction of the Techtiv family of solvents, which
are commercially used to recover BTX at very high
efficiency, with no product contamination.
LLE processes, although reliable and prevalent in
the industry for a long period of time, have not been
able to offer improvements that make them competitive
against the current state-of-the-art ED process. The
configurations for the two processes are shown in Fig. 7.
In the LLE systems, the solvent makes an incomplete
separation of the components at both ends of the
extraction column, thus requiring the additional steps of
extractive stripping and water washing of the raffinate.
In the modern ED system, the ED column cleanly
removes the nonaromatics from the aromatics; and the
aromatics plus solvent from the raffinate in a single
operation. Therefore, the ED design require fewer
pieces of equipment and a much lower capital cost than
a LLE system or other ED systems that require washing
of products, or reprocessing of the raffinate.
H2 O + CH4
CH3
CH3 CH3
O CH3 O + O
CH3 CH3
CH3 CH3
O O + O
CH3
H2 O + C2H6
Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
DOI: 10.1002/apj
276 J. C. GENTRY
Figure 7. Process schemes for LLE and ED. This figure is available in colour
online at www.apjChemEng.com.
HOW TO PRODUCE MORE BENZENE
With the relative imbalance of benzene demand against
a more limited supply, it is important to understand
how more benzene could be produced. The first area to
look for additional production of benzene is the existing
sources. Figure 8 shows the major sources of worldwide
benzene production. Pygas is the largest source of
benzene followed by catalytic reformate and by-product
benzene from paraxylene production (Fig. 8).
Certainly more benzene can be produced, if the over-
all economics of running these operations is favor-
able. Extensions of these processes can also be used
to produce additional benzene. The worldwide supply
situation must be resolved by a multitier approach, con-
sidering the available sources. Several factors influence
the distribution of the sources. For example:
• Hydrodealkylation remains a swing source due to
the variable economic margins between benzene and
the heavier aromatics. Although relatively inefficient,
this route will continue to be an option for benzene
COLO
PX co-product
Pygas
Pygas Reformate
HDA
HDA
PX co-product
COLO
Reformate
Figure 8. Worldwide sources of benzene produc-
tion. This figure is available in colour online at
www.apjChemEng.com.
 2007 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
production considering favorable price differentials
that occur periodically.
• Pygas sources for benzene are diminishing as many
of the new ethylene crackers are based on lighter
feedstocks (which produce less pygas, and hence
less benzene). It is paramount that all benzene
which is produced in steam crackers be recovered
as petrochemical product.
• In the refinery environment, benzene in gasoline is
regulated to below 1 vol% in the EU and US The
rest of the world is moving toward these standards.
There is a great opportunity to extract and purify the
benzene, which increases the petrochemical upgrade,
and also solves the problem of eliminating benzene
in motor fuels. If a refiner has an aromatics extraction
unit, then a change in naphtha cutpoint into the
reformer can favor benzene precursors and lead to
increased benzene production.
ECONOMICS OF BENZENE PRODUCTION
With today’s pricing environment, nearly all production
routes would yield a very good return on investment.
The issue still remains that benzene supply largely
depends on other products. Historically, the benzene
price could be predicted by 1.7× WTI crude oil price.
Today the benzene price is almost double this ratio.
The key is to factor in the correct projections about
the pricing of benzene and other aromatics in order to
correctly put the incentive on the production choices.
CMAI has reported that benzene extraction margins
averaged a phenomenal $456/ton during 2004. Even the
swing production method of HDA averaged $138/ton
(Table 1).
The pricing has been subject to wild gyrations due
to shipping, logistics, and contract settlements, etc. But
Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering BENZENE PRODUCTION AND ECONOMICS 277

Table 1. 2004 US benzene production Table 3. Benzene cost of production (recovery from
margins. Source: CMAI. raw pygas).

Extraction HDA Plant capacity 150 000 tpa benzene

margins margins Feed 650 000 tpa full-
Month $/ton $/ton range RPG
Investment $50 MM
January 165 −75 Raw materials $405 MM
February 214 −28 By-product credits $283 MM
March 223 20 Utilities $16 MM
April 341 41 Fixed + allocated costs $3 MM
May 248 13 Cash cost of benzene production $787/ton
June 392 108 Current benzene pricing $1100/ton
July 576 159 Simple return on investment <15 months
August 767 261
September 741 173
October 591 255
November 635 335
December 573 289 return on investment for benzene production is better
2004 average 456 138 that most other petrochemicals. Similar cases can be
made for other production routes for benzene (Table 3).

Table 2. Aromatics valuation.

CONCLUSIONS

Benzene is a valuable chemical intermediate used for

the spread over feedstock costs has definitely been on
the upswing. Table 2 below shows the petrochemical
value for benzene, toluene and xylenes compared to the
octane blending value in gasoline. In all cases, there
is a tremendous incentive to separate and purify the
petrochemicals (Table 2).
Table 3 shows the overall production economics for
benzene recovery from raw pyrolysis gasoline. The
a range of consumer products. In spite of recent health
warnings, benzene will continue to be in demand for the
foreseeable future. High-purity benzene is not obtain-
able through simple cracking or reforming. Downstream
production requires benzene purities of 99.9%. While
LLE techniques have been used in the past, ED offers
lower capital cost, less complicated operation, flexibility
for feedstock variations, and reliably high-purity prod-
ucts. The key is to use the most efficient solvent system
and design techniques.
As the availability, quality, and uses of hydrocarbon
fuels evolve over the next few decades, chemical pro-
ducers will continue to look at various benzene produc-
tion routes to meet the demand. While variable margins,
diminishing feedstock sources, and the mandated reduc-
tions of benzene in gasoline, all influence the available
amounts and distribution of benzene sources, continu-
ous improvements in technology will allow producers
to access production routes that are economically attrac-
tive. Instead of destroying benzene, producers should
focus on capturing the value of this petrochemical.

 2007 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2007; 2: 272–277
DOI: 10.1002/apj