Dry Gas: China
Summary
Ethylbenzene, used in the production of
many plastics, is derived from benzene and
ethylene. Producing ethylene usually has
required the construction and operation of
an expensive high-temperature plant. An
alternative, cheap source of ethylene is the
so-called “dry gas,” a by-product of gasoline
production, which contains some 20 percent
ethylene. Separation has presented difficul-
ties, however. For this reason, ethylene cre-
ated during the production of gas normally
has been burned off for heat recovery. Now,
a new process using a carefully designed cat-
alyst has provided a high conversion rate of
ethylbenzenefrom the dry gas. Two plants in
China are operatingwith the new technology.
Ethylene is an important raw chemical
substance used all over the world. For
example, polystyrene is produced by the
alkylation of benzene with ethylene - that
is, the reaction of ethylene with benzene to
form ethylbenzene. (Styrene is then pro-
duced from the dehydrogenation of ethyl-
benzene and polystyrene from polymeriza-
tion.) Worldwide, the annualconsumption of
polystyrene for manufacture of plastic com-
modities is some 100 million tonnes.
Ethylene has normally been produced
through high-temperature cracking of
petroleum feedstocks; the plant needed for
this requires enormous financial invest-
ments. However, a cheap source of ethylene
does exist. This is the dry gas produced by
the fluid catalytic cracking (FCC) plants in
petroleum refineries. Such plants, which
VOLUME ONE- SCIENCE AND TECHNOLOGY
convert low-cost heavy petroleum oil into
valuable gasolines, are key installationsin all
refineries.
In addition to the main product gasoline,
FCC plants yield large amounts of by-prod-
uct gases. Among these by-products is “dry
gas” which contains large amounts of nitrc-
gen, carbon dioxide and carbon monoxide
- none of which are useful. The dry gas
also contains about 20 percent volume of
ethylene, which is a valuable chemical s u b
stance. The ethylene, however, is not easy to
separate from the other components and is
normally burned off in the refineries for heat
recovery.
The basis of the innovative experience
described here is the development of new
technologies to exploit the ethylene for use
in the production of ethylbenzene, with s u b
stantial economic benefits. Eight years of
research led scientistsat the Dalian Institute
of Chemical Physics (DICP) in China to
develop a new chemical process for produc-
tion of ethylbenzene that enabled the ethy-
lene sourced from FCC dry gases to react
with benzene. New plants based on this tech-
nology have been built in China for com-
mercialization.
The first of these new plants that use the
technology of direct alkylation of benzene
with FCC dry gas, without any pre-treat-
ment, to produce ethylbenzene was estab-
lished in 1993. The technology is based on a
sophisticated catalyst developed by DICP.
The chemical industry often turns to cata-
lysts as the only route to a certain product. A
43
 DRY GAS: CHINA
catalyst’s “activity” can accelerate the pro-
duction rate of a chemical reaction. At the
same time, its “selectivity”dictates a cata-
lyst’s ability to enhance the production rate
of the desired product and minimize the for-
mation of by-products.
In the first commercial plant based on the
DICP technology, the catalyst’s activity and
selectivity have remained high after five
years of operation. Conversion of the ethy-
lene in the dry gas has exceeded 95 percent,
the selectivity to ethylbenzene has been
more than 99 percent, and the purity of the
ethylbenzene produced has averaged 99.6
percent of its weight. A second plant is oper-
ating with similar results.
Background
and Justification
FCC is an important heavy-oil conversion
technology in refineries. In China, the total
capacity of FCC plants has reached 56 mil-
lion tonnes per year. Dry gas, meanwhile, is
produced at an annual rate of 1.68 million
tonnes. The latter usually contains some 20
percent volume of ethylene that is burned
off as refinery fuel.
To exploit the ethylene in dry gas, DICP
developed a process of direct alkylation of
benzene with the dry gas without any special
pretreatment. Application of this technology
not only allows better exploitation of the
ethylene resources in the FCC dry gas, but
also addresses the problem of shortage of
ethylbenzene in China.
Outside China, processes using dilute
ethylene to produce ethylbenzene have been
developed. All these efforts, however, rely
on pretreatment of the dry gas to remove
44 SHARING INNOVATIVE E X P E R I E N C E S
small amounts of such impurities as hydro-
gen sulfide, carbon dioxide and water vapor.
These impurities could damage the catalyst
and so must be removed if the catalyst is to
maintain a long and stable operational lie.
The unique feature of the DICP technology
is the development of a catalyst that is resis-
tant to sulfur and water and has a long oper-
ational life.
Description
Use of a catalyst with ethylene in the FCC
dry gas to alkylate with benzene to produce
ethylbenzene began in 1985. DICP research,
first on a laboratory scale and then in a pilot
plant, under conditions simulating commer-
cial plants led to development of a novel cat-
alyst for this new technology by 1988. The
next two years saw the manufacture of the
catalyst on a semi-commercial scale (500
tonnes annually). Design of a commercial-
scale plant, with production capacity of
30,000 tonnes per year, then followed, and
the plant was built and put into continuous
operation in 1993.
In the conventional production process of
ethylbenzene, impurities such as hydrogen
sultide, carbon dioxide and water vapor in
the FCC dry gas can lower the ethylbenzene
selectivity and operational life of the catalyst,
and also the quality of the ethylbenzene pro-
duced. To counter these unfavorable effects,
the catalyst was moditied with rare-earth
oxide components during its preparation and
treatment with steam at high temperature.
The new catalyst can be used under a
wide range of reaction temperatures and low
pressures, and allows good benzene alkyla-
tion with the original dry gas. The catalyst
 DRY GAS: E ~ I N A
has a long operational of 90 to 100 days
before requiring regeneration.
The ethylene content in FCC dry gas is
10 to 30 percent of volume. The heat evolved
during the chemical reaction results in a
temperature rise of 60o to 180o C. Multi-
stage reactors are used during the process.
After pre-heating, benzene enters the first
reactor which contains a catalyst and
exchanges heat directly with the high-tem-
perature effluent to absorb the reaction heat.
The problem of heat removal in an adiabatic
reactor is thus solved as the temperature
rise of the inlet and outlet flow is lowered to
between 50" and 70" C. Temperatures in the
various reactors are quite uniform.
Recovery of benzene vapor from the tail
gas reactor effluent is vital to the reduction
of benzene consumption. Because only the
ethylene in the dry gas undergoes reaction,
more than 70 percent of the gas will exit the
reactors as inert gas. The new DICP tech-
nology allows the tail gas benzene to be
absorbed by the reaction raw material, and
gives a recovery rate of at least 99 percent of
weight at room temperature. The gas leav-
ing the absorber is led to the refinery fuel-
gas system.
The catalyst displays good performance
characteristics: high activity, high tolerance
to harmful impurities, long operational life
and easy regeneration. In addition, this pro-
prietary technology possesses several
advantageous features: (1) because the FCC
dry gas needs no pretreatment, the produc-
tion process is simpliied; (2) benzene in the
tail gas can be recovered by passing this gas
through an adsorption tower; (3) the cata-
lyst, a so-called molecular sieve, does not
V O L U M E ONE- SCIENCE A N D T E C H N O L O G Y
generate harmful or poisonous pollutants
during the alkylation reaction; and (4) the
exhaust tail gas can be used as a fuel to the
refineries, making the technology environ-
mentally friendly.
Patenting and
Commercialization
The results of the test operations at the
Fushun Refinery showed a slow decrease of
catalyst activity over time, but constant
selectivity to ethylbenzene and ethylben-
zene purity. In addition, raw material con-
sumption remained constant.
The data from this plant indicate
the average conversion of ethylene to
exceed 95 percent, selectivity to ethylben-
zene to exceed 99 percent, and purity of
ethylbenzene produced to exceed 99.6 per-
cent. Consumption of benzene and ethyl-
benzene was 0.76-0.78 tonnes and 0.270-
0.275 tonnes, respectively, for the production
of 1tonne of ethylbenzene, with overall ener-
gy consumption of about 400 kg-FOE per
tonne ethylbenzene produced.
A detailed specification of the ethylben-
zene produced at the commercial plant indi-
cates that it meets the China National Stan-
dard premium grade and can be used in the
manufacture of styrene, pharmaceuticals
and perfumes.
The plant was put into operation in 1993
at the No. 2 Refinery of the SINOPEC
Fushun Petrochemical Company, and has
been running satisfactorily to date. In
December 1996, a second plant was put into
operation. This plant is located in the
SINOPEC Linyuan Refinery in northern
China. The plant capacity is 30,000 a year.
45
Operational results of this second plant are
similar to those of Refinery No. 2 of the
SINOPEC Fushun Petrochemical Company.
The developers of this new technology
are ready to collaborate with foreign enter-
prises on technology transfer, and to provide
services including:
Project proposals.
Feasibility reports.
Technical consultation.
Basic, preliminary and detailed
designs.
Contracting and procurement
services.
Construction supervising.
Commissioning of new plants.
Personnel training.
Following the initial experience in China,
the developers are confident that the new
technology is especially cost-effective and
suitable for commercialization in other
developing countries.
Partnerships
This new technology has been developed
solely in China. DICP was responsible for
creating the new catalyst, while the design
and process development were the respon-
sibility of the public partnership SINOPEC
Fushun Petrochemical Company.
Replicability
The manufacturing technology of the cata-
lyst has proved satisfactory for commercial-
scale production.
46 S H A R I N G INNOVATIVE EXPERIENCES
Lessons learned
A novel catalyst-based technology for pro-
duction of ethylbenzene by alkylation of ben-
zene with dilute ethylene in FCC dry gas has
been developed and commercialization in
China has begun. The technology is simple
to apply, has significant cost benefits, and is
environmentally friendly.
This technology can allow the ethylene
resources in FCC dry gas to be exploited,
and may also be a solution to the shortage of
ethylbenzene in China.
Outside China, processes using dilute
ethylene to produce ethylbenzene have been
developed, but all rely on pre-treatment of
the dry gas to remove impurities.
Impact
Application of the new technology
through commercialization can bring the
advantages of cleaner and more efficient
industrial processes, with ensuing cost ben-
efit. The technology is now proven on a com-
mercial basis. 0
Implementing Institution:
Dalian Institute of Chemical Physics
Head: Yang Bailing, Director
Address: Chinese Academy of Sciences,
PO. Box 10, 116023, Dalian Zhongshan
Road 457, China
Tel.: 086-411-4671991
Fax: 086-411-4691570
E-mail: <<hyperlinkmailto:lyx>>
Cost: government support US$2 million