See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/268302883

Advances in DCC Process and Catalyst for Propylene Production from Heavy
Oils

Article in China Petroleum Processing and Petrochemical Technology · March 2011

CITATIONS READS

2 1,800

5 authors, including:

Jun Long
Central South University
171 PUBLICATIONS 1,776 CITATIONS

SEE PROFILE

All content following this page was uploaded by Jun Long on 19 November 2015.

The user has requested enhancement of the downloaded file.

 China Petroleum Processing and Petrochemical Technology
Review 2011,Vol. 13, No. 1, pp 1-5 March 30, 2011

Advances in DCC Process and Catalyst for Propylene

Production from Heavy Oils

Liu Yujian; Long Jun; Tian Huiping; Xu Yun; Zhao Liuzhou

(Research Institute of Petroleum Processing, SINOPEC, Beijing 100083)

Abstract: In the past several decades, SINOPEC has devoted continuously great efforts to the development of DCC tech-
nology, the only commercial process using heavy feeds aiming at propylene production. Recently, a series of research
breakthroughs have been achieved in molecular refining. Based on the detailed analysis on the complex DCC reaction
network, an innovative catalyst technology has been developed to Optimize Catalysis Kinetics (OCK in brief). The deep-
cracking process can be improved with optimizing the availability of the active sites. The updated MFI and beta zeolites
are used to boost the propylene selectivity. The latest generation catalyst DMMC-1 has been applied commercially. Com-
pared with the best historical records in the past, the propylene yield upon application of the catalyst DMMC-1 increases
by 2.4 m% coupled with an improved distribution of products. The DCC technology continues to assume a leading posi-
tion for manufacturing propylene from heavy feedstocks.
Key words: petrochemical engineering, propylene, catalytic cracking, catalyst, catalysis kinetics

1 Introduction and propylene production). Among those refining processes,

Amid the increasing market demand and the consequent
competitions among the global refiners, an issue has
emerged for enhancing the production of propylene. In a
very general sense, there are three major technologies for
propylene production[1]. The propylene output from steam
cracking accounts for up to 70% of all propylene produc-
tion, but with this technology the propylene-to-ethylene
ratio is very low, the feedstocks suitable for steam crack-
ing are some light oils that also become less available.
The remaining propylene is manufactured from FCCU
and other processes (propane dehydrogenation, etc.), but
the capacities of propylene production are still limited[2-3].
In order to respond to this challenge, SINOPEC Research
Institate of Petroleum Processing has been devoting it-
self to a series of family technologies for light olefins
production. There are DCC (for maximum propylene
production), MGG (for maximum LPG plus naphtha
production), MIO (for maximum iso-olefins and naphtha
production), CPP (for maximum ethylene and propylene
production), and MIP-CGP (for maximum clean gasoline
DCC is the only commercial process in the world using
heavy feeds for propylene production. With the specific
feed and suitable operation, the propylene yield of DCC has
reached up to 20%.
The first DCC unit has been demonstrated in 1990 and
commercialized since 1994. Eight units have been put
into operation in China and overseas. In the Middle East,
a new unit at Petro-Rabigh has been set up and com-
missioned in more than one year. The DCC process has
succeeded to be a more and more profitable technology,
indicating to a rosy future for the refining and petrochemi-
cal industry. As a result of this achievement, recently DCC
technology is making very rapid progress in many coun-
tries. The DCC process and catalyst have already become
the focus and the hotspot of R&D in many famous cata-
lyst companies[4-5]. SINOPEC had to realize such a fact,
that further innovations in DCC should be urgent to keep
up its leading position[6].
Corrresponding Author: Dr. Liu Yujian, Telephone: +86-10-
82368378; E-mail: liuyj.ripp@sinopec.com

· 1·
China Petroleum Processing and Petrochemical Technology 2011,13(1):1-5

2 RIPP’s Advances in DCC Process Table 1 Some global refiners with DCC commercial units
Location Capacity, kt/a Startup Date/Status
From the view of the process scheme in Figure 1, DCC
Jinan, China 60 Nov. 1990
process is very similar to conventional FCC process, but the
Jinan, China 150 Jun. 1994
operating condition of DCC process is regulated to realize
deep cracking reactions, so the DCC unit has more severity Anqing, China 650 Mar, 1995

on operating condition compared to that of FCC process. Daqing, China 120 May, 1995

IRPC (TPI), Thailand 1 000 May, 1997

Jingmen, China 800 Sept. 1998

Shenyang, China 500 Oct. 1998

Jinzhou, China 300 Sept.1999

Blue Star, China 500 Oct. 2006

Aramco, Saudi Arabia 4 500 May, 2009

3 R IPP’s Advances in DCC Catalyst

Figure 1 Overview of the reactor & regenerator system of
FCCU and DCCU.
The DCC process has two operating modes to meet cus-
tomer’s different requirements. DCC-I aims at a maxi-
mum propylene mode, and DCC-II aims at a mode for
maximum propylene plus iso-olefins and naphtha yields.
The DCC feedstocks have been extended to heavy oils,
just like the FCC feedstock. Compared with the FCC
process, the DCC process features higher reaction tem-
perature, higher catalyst-to-oil ratio, longer residence
time, lower hydrocarbon pressure and more steam injec-
tion. The reactor type of DCC unit consists of a riser or a
combination of riser and bed. DCC’s fractionator needs a
higher vapor-to-liquid ratio, and its compressor capacity
is also larger. With respect to the product distribution, the
propylene yield of DCC process is 3 or 5 times more than
that of FCC process, with increased isobutylene yield,
and decreased naphtha and LCO yields.
From 1990 to present day, many DCC commercial units
listed in Table 1 have been put into production. According
to the owner’s wish, some process mode is the DCC-II,
such as the DCCU in Shenyang, China. If necessary, this
mode can be switched to DCC-I very flexibly. Another
DCCU, such as the one owned by Blue Star, China, is of
the DCC-I mode, which can also be switched to DCC-II
as the market need changes.
Development
Thanks to the strenuous efforts on catalysis study made
by several generations of research staff in RIPP, the DCC
catalysts also have been improving generation after gen-
eration. The 1st generation of DCC catalysts was the CHP
series, which were seeking for high propylene selectivity.
The 2nd generation catalysts, the CRP and CIP series,
had high hydrothermal stability and increased bottoms
cracking capability. The MMC catalysts have higher pro-
pylene selectivity and metals tolerance. Today the MMC
catalysts have been applied in most DCC units. Recently,
the latest generation catalyst DMMC-1 has already been
developed and adopted in commercial application[7].
The CHP/CRP/CIP series catalysts have high matrix ac-
tivity for bottoms primary cracking reactions. A mesopo-
rous zeolite has been used for further secondary cracking
reactions. The isomerization performance of the catalyst
is indispensable, and the hydrogen transfer reactions need
to be controlled. With the same generation catalyst, the
light olefin yields from different feed oils are listed in
Table 2. Refinery A had the highest propylene yield, 23
m% from the feed originating from a typical paraffinic-
base oil. Propylene yields at refineries B, C, and D were
a little lower from feeds originating from intermediate-
base oil. It was reported that an increase in aromaticity of
a feedstock would result in a decrease in propylene yield.

· 2·
 Liu Yujian, et al. Advances in DCC Process and Catalyst for Propylene Production from Heavy Oils

Table 2 DCC light olefin yields from different feeds lytic components. The new preparation technology has
Refinery A B C D been developed aiming to improve the bottoms cracking
Feedstock VGO+ATB VGO VGO+DAO VGO+DAO capability and to optimize the availability of the active
Feedstock
sites. Because the DCC process is regulated with a series
type Paraffinic Intermediate Intermediate Intermediate of cracking reactions in a specific sequence, the large-size
Ethylene, molecules can be cracked to smaller ones in sequence
m% 3.7 3.5 5.3 5.3
when accessing a series of pores and active sites. In this
Propylene,
m% 23.0 18.6 18.5 19.2 DCC catalysis mechanism, the catalyst with macroporous
Butylenes, structure is conducive for the cracking of large-size mol-
m% 17.3 13.8 13.3 13.2 ecules, and the catalyst with higher availability of active
sites can boost deep-cracking reactions. Actually, this
The MMC series catalysts have enhanced propylene se- catalyst designing concept is related to optimizing cataly-
lectivity and metal tolerance by using ZSP zeolite as the sis kinetics, so we called it OCK technology briefly[8].
main active component. The MMC catalysts have been Figure 2 is the BET absorption curves of the fresh cata-
commercialized at several refineries at home and abroad. lysts. The cumulative pore volume of the DMMC-1 cata-
The results of catalyst pilot plant testing are presented in lyst is higher than that of the MMC catalyst. When treated
Table 3. Compared with the reference catalyst, the MMC by steaming, the DMMC-1 catalyst can retain higher pore
catalyst has deeper cracking performance and increased volume.
propylene yield. The propylene content in cracking gas
becomes higher.
The MMC-1 catalyst is developed for the customers who
want to increase the propylene yield as well as the LPG
yield. The MMC-2 catalyst is developed for the custom-
ers who want to increase the propylene yield albeit with
less LPG yield.

Table 3 Pilot plant testing of MMC catalysts

Items CIP MMC-1 MMC-2

Dry gas yield, m% Base +0.5 -0.8

LPG yield, m% Base +2.2 -0.3

Naphtha yield, m% Base -2.7 +2.1

Propylene in total gas, m% Base +0.7 +3.3

Propylene yield, m% Base +1.3 +1.0

4 Innovations on the Latest Generation

DCC Catalyst
Recently, more innovations have been applied to the
Figure 2 The N2 absorption results (BET) of fresh catalysts
DCC catalyst. The latest generation catalyst DMMC-1
(top) and catalysts after steaming (bottom)
has been developed for higher propylene yield, improved
distribution of products and better gasoline quality. There The catalysts test data are listed in Table 4. Compared with
are two major innovations in DMMC-1 catalyst, i. e.: the the MMC-2 catalyst, the DMMC-1 catalyst has more pore
new preparation technology of catalyst and novel cata- volume and more surface area. These features reveal that

· 3·
China Petroleum Processing and Petrochemical Technology 2011,13(1):1-5

the macroporous structure design has been realized by Table 5 Pilot plant testing of DMMC-1 catalyst and
OCK technology. MMC-2 catalyst
Items MMC-2 DMMC-1
Table 4 BET data of the catalysts
Dry gas yield, m% 6.87 7.23
Items MMC-2 DMMC-1
LPG yield, m% 39.30 40.53
Fresh catalyst
Gasoline yield, m% 28.42 27.16
VH2O, mL/g Base Base+21%
Naphtha yield, m% 11.32 11.36
VBET, mL/g Base Base+13%
LCO yield, m% 6.99 6.91
Aged catalyst
Slurry yield, m% 7.10 6.81
SBET, m2/g Base Base+19%
Conversion yield, m% 81.69 81.72
VBET, mL/g Base Base+13%
Ethylene yield, m% 3.92 4.36

Figure 3 shows the electron microphotographs of cata- Propylene yield, m% 15.94 18.19
lysts magnified 30 000 times by a scanning electron- Butylenes yield, m% 10.55 10.99
microscope. The surface of MMC-2 catalyst is less per-
C2=+C3=+C4= yield, m% 30.41 33.54
meable; however, the surface of the DMMC-1 catalyst is
Isobutylene yield, m% 4.32 4.57
porous and permeable. As a result, the surface structure
of the DMMC-1 catalyst has more active sites than that of Propylene selectivity, % 19.5 22.2

the MMC-2 catalyst. Thus higher active sites availability Olefins in gasoline, v% 26.91 24.68
has been realized by OCK technology.
The catalyst pilot plant testing results are presented in Upon summing up the test results relating to DMMC-1
Table 5. Compared with the MMC-2 catalyst, the pro- catalysts the propylene yield increased by 2.43 m%, and
pylene yield of the DMMC-1 catalyst increased from the total liquid yield increased by 0.64 m%, with the ole-
15.94% to 18.19%, with improved propylene selectivity fins content in gasoline plummeting by 4.5 v%. The dis-
and bottoms cracking capability. The olefins content in tribution of products has been improved with the DMMC-1
gasoline decreased. The commercial application data gave catalyst.
the same results as indicated in Table 6. Propylene and
Table 6 Commercial application of DMMC-1 and
LPG yields increased, and the bottoms cracking capabil-
MMC-2 catalysts
ity became better. The total liquid yields also increased.
Items MMC-2 DMMC-1
Additionally, the coking selectivity of DMMC-1 catalyst
Product yield, m%
was improved. The quality of gasoline had been proved to
Dry gas 7.71 7.89
be better during commercial application. Just like the pi-
LPG 34.60 38.90
lot plant results, the olefins content in gasoline decreased
from 43.7% to 39.2%. Naphtha 29.90 26.09

LCO 19.42 19.57

Slurry 0.25 0.00

Coke 7.61 7.05

Propylene yield, m% 15.37 17.80

Butylenes yield, m% 12.60 13.01

C2 +C3 +C4 yield, m%

= = =
30.66 33.92

Liquid yields, m% 83.92 84.56

Figure 3 SEM photographs of MMC-2 catalysts and
Olefins in gasoline, v% 43.7 39.2
DMMC-1 catalysts

· 4·
 Liu Yujian, et al. Advances in DCC Process and Catalyst for Propylene Production from Heavy Oils
4 Future Developments of DCC Tech-
nology
However, the future progress of DCCU will be expected
further, both in the area of unit operation and research
activities. These developments will be focused on the fol-
lowing.
Concerning the unit operation:
1) Heavier feedstock should be processed.
2) Mild operation condition should be adopted to lower
dry gas yield while maintaining the same propylene yield.
Concerning the R&D activities related with the DCC pro-
cess:
1) Establish petrochemicals-based refining technology in
pursuit of maximizing yields of propylene, ethylene and
light aromatics as by-products.
2) On the basis of fluid catalytic cracking technology, the
propylene yield of future DCC process will be 6—8 times
that of conventional FCC process, and the total yield of
propylene plus ethylene will be equal to that of steam crack-
ing process. New types of reactors and catalysts will be de-
signed.
3) Lower value stream, such as C4 fractionate, lighter
gasoline, even LCO will be recycled to mainly produce
propylene, with ethylene obtained as by-product.
4) Heavy gasoline fraction will be used as the feedstock
for aromatics extraction to obtain blending components
rich in xylene.
5 Conclusions
(1) DCC is an attractive technology for propylene produc-
tion using heavy feeds, which can successfully integrate
oil refining with petrochemical industry.
(2) The feedstock can be extended to inferior oil, even
residue oil.
(3) Recent innovations on novel catalytic materials have
been used to increase propylene selectivity, and new cata-
lyst manufacturing technology has made further strides
in increasing propylene yield by improving the bottoms
cracking ability.
(4) With advanced characterization techniques and care-
View publication stats
ful catalyst formulation design, the DCC catalyst can be
tailor-made to meet special requirements for processing
heavier feedstocks.
Several decades of experience in commercialization of
DCCU have made the DCC technology nearly perfect,
mature and promising. Relentless R&D activities and in-
novations on DCC technology are continuing to assume
a leading position in light olefins production using heavy
oil as the feedstock.
References
[1] Song Zhaozheng, Zhao Mifu, Ge Jijiang, et al. Advances in
low-carbon olefins production technology[J]. Advances in
Specialty Petrochemicals, 2004, 5(2): 42-48 (in Chinese)
[2] Qiao Yingbin, Duan Qiwei. New advances in petrochemical
technologies[J]. Chemical Industry and Engineering Prog-
ress, 2003, 22(2): 109-113 (in Chinese)
[3] Jakkula J, Hiltunen J, Niemi V, et al. A novel circulating fluid-
ized bed reactor system for chemical reactions[J]. ACS Division
of Petroleum Chemistry, 1999, 44(4): 460-462
[4] Niccum P K, Bhore N A, Miller R B, et al. MAXOFINTM:
A novel FCC process for maximizing light olefins using a
new generation of ZSM-5 additive[C]. NPRA 1998 Annual
Meeting, AM-98-18
[5] H emler C L, Upson L L. Maximising FCC propylene
production[J]. Petroleum Technology Quarterly, 1999, 4(2):
31-35
[6] Liu Yujian, Long Jun, Tian Huiping. Innovations in DCC
catalyst for propylene production from heavy oils[M]//Hong
Dingyi. Technical Progress in Refining and Petrochemical
Industry. Beijing: China Petrochemical Press, 2010: 310-
325 (in Chinese)
[7] Long Jun, Tian Huiping, Liu Yujian, et al. Study on the
performance and commercial application of new generation
DMMC-1 type catalyst for deep catalytic cracking[J]. China
Petroleum Processing and Petrochemical Technology, 2007,
(4): 1-6
[8] Long Jun, Tian Huiping, Zhang Weilin, et al. A kind of
zeolite-containing catalyst for hydrocarbon cracking and its
preparation method: Chinese Patent Appl, 03147987.1[P].
2003-06-30
· 5·