Catalysis Surveys from Japan Vol. 4, No.

2, 2000 157

Catalytic cracking of naphtha to light olefins

Y. Yoshimura a,∗ , N. Kijima a , T. Hayakawa a , K. Murata a , K. Suzuki a , F. Mizukami a , K. Matano b , T. Konishi b ,
T. Oikawa b , M. Saito b , T. Shiojima b , K. Shiozawa b , K. Wakui b , G. Sawada b , K. Sato b , S. Matsuo b and N. Yamaoka b
a National Institute of Advanced Industrial Science and Technology∗∗ , Tsukuba, Ibaraki 305-8565, Japan
E-mail: y.yoshimura@aist.go.jp
b Japan Chemical Industry Association, Kasumigaseki 3-2-4, Tokyo 100-0013, Japan

A catalytic process that produces light olefins from naphtha was developed to improve the yield of the conventional steam cracker. In
laboratory-scale tests, a newly developed zeolite-based catalyst at a reaction temperature of 650 ◦ C produced an ethylene-plus-propylene
yield of about 60%, which is about 10% higher than the conventional process operated at around 820 ◦ C. A feasibility study carried out
for a catalytic cracking process using the developed catalyst, that cracks 3 000 tons-naphtha/day, indicated an energy saving of about 20%
compared with the conventional process.
KEY WORDS: naphtha; catalytic cracking; light olefins; oxidative cracking; rare earth/ZSM-5 catalyst; feasibility study

1. Introduction for the petrochemical association, because it can take advan-

tage of the existing facilities that are used for steam cracking.
Basic chemicals such as ethylene, propylene, and other R&D on catalytic cracking of hydrocarbons including
light olefins are currently manufactured mainly from naph- naphtha to light olefins started in the late 1960s. The cat-
tha by thermal cracking, i.e., so-called steam cracking. To alysts are typically classified into three-types, i.e., acidic
cope with the requirements of higher-temperature and re- catalysts, basic catalysts and transition metal oxide cata-
duced residence time, the steam cracking process has been lysts, which are used under the non-aerobic or aerobic con-
modified in various ways to improve energy efficiency, e.g., ditions (table 2). In comparison with the conventional steam
the cracking furnace (radiant tube and coils) and heat re- cracking, acidic catalysts such as Ag-mordenite/Al2O3 [2],
covery systems. However, marginal technological improve- Cu/HZSM-5 [3] and hydrothermally treated HZSM-5 [4]
ments cannot make further improvement in energy effi- gave low ethylene but high propylene and aromatics yields
ciency. The current steam cracking process uses as much at lower temperatures under the non-aerobic conditions. Re-
as 40% of the energy consumed by the entire petrochemical cently, SINOPEC Research Institute of Petroleum Process-
industry. Therefore, global environmental issues have stim- ing (RIPP) in China succeeded in increasing the yields of
ulated the development of processes that maximize energy- light olefins over proprietary zeolite catalysts by convert-
and resource-savings and minimize CO2 emissions. Besides, ing heavy feedstock to light olefins, LPG and naphtha [5].
in the case of the current steam cracking process, it is diffi- However, in order to enhance the yields of light olefins (e.g.,
cult to control the composition of olefins formed. Hence, from naphtha), aromatization reactions which are fast over
there is an increasing demand for processes capable of con- fluidized catalytic cracking (FCC) catalysts should be mini-
trolling the composition of olefins. mized.
Catalytic cracking over basic catalysts such as CaO–SrO–
To respond to these needs, an association of 12 petro-
Al2 O3 [6], WO3 –K2 O–Al2 O3 [7] and KVO3 /corundum [8]
chemical companies which have olefin centers in Japan, have
started an R&D project on naphtha catalytic cracking to re-
place steam cracking (figure 1). Despite numerous patents
on naphtha catalytic cracking, none of the naphtha catalytic
cracking processes have been used in commercial olefin pro-
duction. Nevertheless, research and development has been
continued on naphtha catalytic cracking for the production
of olefins, in particular ethylene, to achieve better olefin
yield and lower energy consumption (table 1 [1]). In ad-
dition, uses of alternative feedstocks such as methane, LPG,
gas oil, crude oil and ethanol have also been pursued. How-
ever, the conventional naphtha is a most attractive feedstock
∗ To whom correspondence should be addressed.
∗∗ These works were carried out in the former organization of National In-
stitute of Materials and Chemical Research. Figure 1. Catalytic cracking of naphtha to light olefins.

1384-6574/01/0700-0157$18.00/0  2001 Plenum Publishing Corporation

158 Y. Yoshimura et al. / Catalytic cracking of naphtha to light olefins

Table 1
Olefin production processes.

Table 2
Reported catalytic performances in naphtha cracking to olefins.

Reaction atmosphere
Non-aerobic Non-aerobic Aerobic/non-aerobic

Type of catalysts Acidic catalysts Basic catalysts Transition metal oxides/

basic catalysts
Temperature (◦ C) 550–650 750–850 500–800
Steam/oil ratio (wt base) 0–1 1–2 0.5–1
Yields of products (wt%)
Ethylene 15–27 30–40 20–50
Propylene 15–50 15–22 3–10
Aromatics 11–34 0 –
CO,CO2 Neg. 5–20 15–30
Examples of catalysts Ag-MOR/Al2 O3 [2] CaO–SrO–Al2 O3 [6] Cr2 O3 /Al2 O3 [9]
Cu/HZSM-5/P [3] WO3 –K2 O–Al2 O3 [7]
Steamed HZSM-5 [4] KVO3 /corundum [8]

with steaming conditions is believed to follow a free rad-
ical mechanism. The catalyst surface probably forms free
radicals at a temperature lower than the conventional steam
cracking, but simultaneously quenches some of formed free
radicals. Compositions of light olefins produced over the
basic catalysts suggest the presence of a radical chain re-
action in the furnace tube and in the void space between
the catalyst particles. Among the catalytic cracking us-
ing basic catalysts, the Vniios (All-Union Research Insti-
tute for Organic Synthesis) process gives the highest olefin
yield such as 38 wt% ethylene and 14.5 wt% propylene over
KVO3 /corundum [8] at 780 ◦C. However, high reaction tem-
perature (770–820 ◦C) and high feed-rate of steam may de-
crease the energy efficiency of light olefin production from
naphtha.
In contrast, catalytic cracking over non-reducible tran-
sition metal oxide catalysts such as Cr2 O3 /Al2 O3 [9] un-
der aerobic conditions, i.e., oxidative catalytic cracking, is
believed to follow a free radical mechanism, where acti-
vated oxygen species abstract hydrogen from hydrocarbons
to form radicals. High yields of ethylene are expected ac-
cording to patents, but the precise control of combustion re-
actions is necessary. In general, the advantages of oxidative
catalytic cracking are to shift the equilibrium and to lower
the furnace temperature due to partial supply of heat by com-
bustion reactions. Using lattice oxygen of the reducible tran-
sition metal oxide catalysts is another option for oxidative
catalytic cracking of naphtha.
Figure 2 illustrates the performance of these typical cata-
lysts, that is, rare earth oxide catalysts, transition metal ox-
ide catalysts, and acidic catalysts, in the catalytic cracking
of alkanes (including naphtha) to produce light olefins. The
x-axis shows the acidic–basic properties of catalysts, and
the y-axis the oxidizing–reducing atmosphere in the work-
ing conditions. The performances of the respective catalysts
will be described later in more detail.
In 1994, the association published a report on a jointly
conducted feasibility study of the naphtha catalytic crack-