Gas: China: Volume One-Scienceand Technology

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Dry Gas: China

Summary convert low-cost heavy petroleum oil into


Ethylbenzene, used in the production of valuable gasolines, are key installationsin all
many plastics, is derived from benzene and refineries.
ethylene. Producing ethylene usually has In addition to the main product gasoline,
required the construction and operation of FCC plants yield large amounts of by-prod-
an expensive high-temperature plant. An uct gases. Among these by-products is “dry
alternative, cheap source of ethylene is the gas” which contains large amounts of nitrc-
so-called “dry gas,” a by-product of gasoline gen, carbon dioxide and carbon monoxide
production, which contains some 20 percent - none of which are useful. The dry gas
ethylene. Separation has presented difficul- also contains about 20 percent volume of
ties, however. For this reason, ethylene cre- ethylene, which is a valuable chemical s u b
ated during the production of gas normally stance. The ethylene, however, is not easy to
has been burned off for heat recovery. Now, separate from the other components and is
a new process using a carefully designed cat- normally burned off in the refineries for heat
alyst has provided a high conversion rate of recovery.
ethylbenzenefrom the dry gas. Two plants in The basis of the innovative experience
China are operatingwith the new technology. described here is the development of new
Ethylene is an important raw chemical technologies to exploit the ethylene for use
substance used all over the world. For in the production of ethylbenzene, with s u b
example, polystyrene is produced by the stantial economic benefits. Eight years of
alkylation of benzene with ethylene - that research led scientistsat the Dalian Institute
is, the reaction of ethylene with benzene to of Chemical Physics (DICP) in China to
form ethylbenzene. (Styrene is then pro- develop a new chemical process for produc-
duced from the dehydrogenation of ethyl- tion of ethylbenzene that enabled the ethy-
benzene and polystyrene from polymeriza- lene sourced from FCC dry gases to react
tion.) Worldwide, the annualconsumption of with benzene. New plants based on this tech-
polystyrene for manufacture of plastic com- nology have been built in China for com-
modities is some 100 million tonnes. mercialization.
Ethylene has normally been produced The first of these new plants that use the
through high-temperature cracking of technology of direct alkylation of benzene
petroleum feedstocks; the plant needed for with FCC dry gas, without any pre-treat-
this requires enormous financial invest- ment, to produce ethylbenzene was estab-
ments. However, a cheap source of ethylene lished in 1993. The technology is based on a
does exist. This is the dry gas produced by sophisticated catalyst developed by DICP.
the fluid catalytic cracking (FCC) plants in The chemical industry often turns to cata-
petroleum refineries. Such plants, which lysts as the only route to a certain product. A

VOLUME ONE- SCIENCE AND TECHNOLOGY 43


DRY GAS: CHINA

catalyst’s “activity” can accelerate the pro- small amounts of such impurities as hydro-
duction rate of a chemical reaction. At the gen sulfide, carbon dioxide and water vapor.
same time, its “selectivity”dictates a cata- These impurities could damage the catalyst
lyst’s ability to enhance the production rate and so must be removed if the catalyst is to
of the desired product and minimize the for- maintain a long and stable operational lie.
mation of by-products. The unique feature of the DICP technology
In the first commercial plant based on the is the development of a catalyst that is resis-
DICP technology, the catalyst’s activity and tant to sulfur and water and has a long oper-
selectivity have remained high after five ational life.
years of operation. Conversion of the ethy-
lene in the dry gas has exceeded 95 percent, Description
the selectivity to ethylbenzene has been Use of a catalyst with ethylene in the FCC
more than 99 percent, and the purity of the dry gas to alkylate with benzene to produce
ethylbenzene produced has averaged 99.6 ethylbenzene began in 1985. DICP research,
percent of its weight. A second plant is oper- first on a laboratory scale and then in a pilot
ating with similar results. plant, under conditions simulating commer-
cial plants led to development of a novel cat-
Background alyst for this new technology by 1988. The
and Justification next two years saw the manufacture of the
FCC is an important heavy-oil conversion catalyst on a semi-commercial scale (500
technology in refineries. In China, the total tonnes annually). Design of a commercial-
capacity of FCC plants has reached 56 mil- scale plant, with production capacity of
lion tonnes per year. Dry gas, meanwhile, is 30,000 tonnes per year, then followed, and
produced at an annual rate of 1.68 million the plant was built and put into continuous
tonnes. The latter usually contains some 20 operation in 1993.
percent volume of ethylene that is burned In the conventional production process of
off as refinery fuel. ethylbenzene, impurities such as hydrogen
To exploit the ethylene in dry gas, DICP sultide, carbon dioxide and water vapor in
developed a process of direct alkylation of the FCC dry gas can lower the ethylbenzene
benzene with the dry gas without any special selectivity and operational life of the catalyst,
pretreatment. Application of this technology and also the quality of the ethylbenzene pro-
not only allows better exploitation of the duced. To counter these unfavorable effects,
ethylene resources in the FCC dry gas, but the catalyst was moditied with rare-earth
also addresses the problem of shortage of oxide components during its preparation and
ethylbenzene in China. treatment with steam at high temperature.
Outside China, processes using dilute The new catalyst can be used under a
ethylene to produce ethylbenzene have been wide range of reaction temperatures and low
developed. All these efforts, however, rely pressures, and allows good benzene alkyla-
on pretreatment of the dry gas to remove tion with the original dry gas. The catalyst

44 SHARING INNOVATIVE E X P E R I E N C E S
DRY GAS: E ~ I N A

has a long operational of 90 to 100 days generate harmful or poisonous pollutants


before requiring regeneration. during the alkylation reaction; and (4) the
The ethylene content in FCC dry gas is exhaust tail gas can be used as a fuel to the
10 to 30 percent of volume. The heat evolved refineries, making the technology environ-
during the chemical reaction results in a mentally friendly.
temperature rise of 60o to 180o C. Multi-
stage reactors are used during the process. Patenting and
After pre-heating, benzene enters the first Commercialization
reactor which contains a catalyst and The results of the test operations at the
exchanges heat directly with the high-tem- Fushun Refinery showed a slow decrease of
perature effluent to absorb the reaction heat. catalyst activity over time, but constant
The problem of heat removal in an adiabatic selectivity to ethylbenzene and ethylben-
reactor is thus solved as the temperature zene purity. In addition, raw material con-
rise of the inlet and outlet flow is lowered to sumption remained constant.
between 50" and 70" C. Temperatures in the The data from this plant indicate
various reactors are quite uniform. the average conversion of ethylene to
Recovery of benzene vapor from the tail exceed 95 percent, selectivity to ethylben-
gas reactor effluent is vital to the reduction zene to exceed 99 percent, and purity of
of benzene consumption. Because only the ethylbenzene produced to exceed 99.6 per-
ethylene in the dry gas undergoes reaction, cent. Consumption of benzene and ethyl-
more than 70 percent of the gas will exit the benzene was 0.76-0.78 tonnes and 0.270-
reactors as inert gas. The new DICP tech- 0.275 tonnes, respectively, for the production
nology allows the tail gas benzene to be of 1tonne of ethylbenzene, with overall ener-
absorbed by the reaction raw material, and gy consumption of about 400 kg-FOE per
gives a recovery rate of at least 99 percent of tonne ethylbenzene produced.
weight at room temperature. The gas leav- A detailed specification of the ethylben-
ing the absorber is led to the refinery fuel- zene produced at the commercial plant indi-
gas system. cates that it meets the China National Stan-
The catalyst displays good performance dard premium grade and can be used in the
characteristics: high activity, high tolerance manufacture of styrene, pharmaceuticals
to harmful impurities, long operational life and perfumes.
and easy regeneration. In addition, this pro- The plant was put into operation in 1993
prietary technology possesses several at the No. 2 Refinery of the SINOPEC
advantageous features: (1) because the FCC Fushun Petrochemical Company, and has
dry gas needs no pretreatment, the produc- been running satisfactorily to date. In
tion process is simpliied; (2) benzene in the December 1996, a second plant was put into
tail gas can be recovered by passing this gas operation. This plant is located in the
through an adsorption tower; (3) the cata- SINOPEC Linyuan Refinery in northern
lyst, a so-called molecular sieve, does not China. The plant capacity is 30,000 a year.

V O L U M E ONE- SCIENCE A N D T E C H N O L O G Y 45
Operational results of this second plant are Lessons learned
similar to those of Refinery No. 2 of the A novel catalyst-based technology for pro-
SINOPEC Fushun Petrochemical Company. duction of ethylbenzene by alkylation of ben-
The developers of this new technology zene with dilute ethylene in FCC dry gas has
are ready to collaborate with foreign enter- been developed and commercialization in
prises on technology transfer, and to provide China has begun. The technology is simple
services including: to apply, has significant cost benefits, and is
Project proposals. environmentally friendly.
Feasibility reports. This technology can allow the ethylene
Technical consultation. resources in FCC dry gas to be exploited,
Basic, preliminary and detailed and may also be a solution to the shortage of
designs. ethylbenzene in China.
Contracting and procurement Outside China, processes using dilute
services. ethylene to produce ethylbenzene have been
Construction supervising. developed, but all rely on pre-treatment of
Commissioning of new plants. the dry gas to remove impurities.
Personnel training.
Impact
Following the initial experience in China, Application of the new technology
the developers are confident that the new through commercialization can bring the
technology is especially cost-effective and advantages of cleaner and more efficient
suitable for commercialization in other industrial processes, with ensuing cost ben-
developing countries. efit. The technology is now proven on a com-
mercial basis. 0
Partnerships
This new technology has been developed
solely in China. DICP was responsible for Implementing Institution:
creating the new catalyst, while the design Dalian Institute of Chemical Physics
and process development were the respon- Head: Yang Bailing, Director
sibility of the public partnership SINOPEC Address: Chinese Academy of Sciences,
Fushun Petrochemical Company. PO. Box 10, 116023, Dalian Zhongshan
Road 457, China
Replicability Tel.: 086-411-4671991
The manufacturing technology of the cata- Fax: 086-411-4691570
lyst has proved satisfactory for commercial- E-mail: <<hyperlinkmailto:lyx>>
scale production. Cost: government support US$2 million

46 S H A R I N G INNOVATIVE EXPERIENCES

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