Deep Catalytic Cracking（DCC）

Introduction
Propylene, only next to ethylene, is one of the most fundamental petrochemical raw materials. Recently,
the world demand for propylene has been increasing rapidly and the annual growth percentage of
propylene is even higher than that of ethylene. As a co-product of steam cracking with its yield
approaching half of the ethylene yield, propylene from steam cracking cannot keep up with the required
propylene/ethylene balance. R&D for increasing propylene production from heavy hydrocarbons has
been carried out actively in the oil refining and petrochemical fields. Deep Catalytic Cracking technology
(DCC), developed by SINOPEC, broke the limitation of conventional FCC process and can doubly
increase the yield of propylene, and has been highlighted in the oil refining and petrochemical industries.
Process Description
Deep Catalytic Cracking（DCC）is a catalytic conversion technology which uses heavy hydrocarbon
feedstocks, such as VGO, VTB or VGO blended with DAO to produce light olefins(ethylene, propylene
and butylenes), LPG, gasoline, and middle distillates etc. The technology mainly targets maximizing
production of propylene (DCC-Ⅰ) or maximizing production of iso-olefins (DCC-Ⅱ). The process
scheme of DCC is similar to that of conventional FCC consisting of reaction-regeneration, fractionation
and gas concentration sections. Feedstock dispersed with steam is fed to the system, then contacted with
the hot regenerated catalyst either in a riser plus fluidized dense bed reactor (for DCC-Ⅰ) or in a riser
reactor (for DCC-Ⅱ) and is catalytically cracked. Reactor effluent proceeds to the fractionation and gas
concentration sections for stream separation and further recovery. The coke deposited catalyst is stripped
with steam and transferred to a regenerator where air is introduced and the coke on the catalyst is removed
by combustion. The hot regenerated catalyst is returned to the reactor at a controlled circulation rate to
achieve the heat balance of the system. The schematic diagram of DCCU reaction-regeneration system is
listed in Figure 1.
 Figure 1 The schematic diagram of DCCU reaction-regeneration system

Features of Technology
Characteristics of Technology
 DCC has two reactor operating modes: DCC-I ( Riser plus fluidized dense bed reactor,
maximum propylene operation mode) and DCC-II ( Riser reactor, maximum isoolefins
operation mode ). DCC can process different heavy feeds (VGO, deasphalted oil, coker gas
oil, atmospheric residue, vacuum residue, etc.), and paraffinic feedstocks are the best feeds
for DCC. In DCC-I mode, over 20wt% propylene yield can be obtained from paraffinic
feedstocks. The naphtha and middle distillates streams from DCC unit can be used as
blending components of high octane number commercial gasoline and fuel oil, respectively.
 As employing specially designed and patented zeolite catalysts, the reaction temperature
of DCC is higher than that of conventional FCC, but much lower than that of steam cracking.
 Flexibility of process operation. Easy to obtain the shift of DCC operation modes by
regulating the operating conditions and catalyst formulations.
 Easy of separation and recovery of product streams through a similar
absorption/fractionation system of conventional FCC. It is not necessary to use cryogenic
separation system of steam cracking for the separation and recovery of DCC product stream.
 Impurity hydrocarbons are trace in DCC lighter olefin products, and hydrotreating is not
needed.
Table1lists general comparison between DCC and FCC, and a block flow diagram of DCC
complex is shown in Figure 2.

Table 1 General comparison between DCC and FCC

Process FCC DCC
Feedstock A wide range of heavy oils A wide range of heavy oils
preferably paraffinics
Catalyst Various types of Y zeolite A modified pentasil structure
catalyst zeolite containing catalyst
Hardware
Reactor Riser Riser and/or bed
Regenerator Base Similar
Main fractionator Base Higher vapor/liquid ratio
Stabilizer/absorber Base Bigger
Compressor Base Larger capacity
Operating conditions
Reaction temp. Base Higher by 30~50oC
Regeneration temp. Base Similar
Cat/oil ratio Base 1.5~2 times
Residence time Base More
Oil partial pressure Base Lower
Dilution steam Base More

To diesel blending

Gas Ethylene Ethylene

Purificat. recovery To ethylene plant
unit

Light
ends unit Propylene To storage

C3 & C4 C3 cut C3
Purificat.& split splitter
LPG to storage
C4
cut Gasoline
Fractionator selective
H2 Other hydrogen. Gasoline
feeds
Vacuum H2
gas oil VGO DCC reactor C4 cut to MTBE plant
HTU & regenerator
Decanted oil to fuel

Figure 2. Block flow diagram of DCC complex

Performances
Reaction temperature is one of the most important factors in the cracking reactions. In
comparison with pyrolysis, DCC can significantly reduce the cracking temperature via the
reduction of cracking activation energy by using the specially designed catalyst. The
optimum reaction temperature of DCC is normally within the range of 520～580oC varying
with the crackability of the feedstocks and the required product slates, and DCC-I (maximum
propylene mode) and DCC-II (maximum iso-olefin mode ) employ the upper range and the
lower range of the above-mentioned temperatures, respectively.
The crackability of the feedstocks can have great effect on the operation parameters and the
product slates. The higher UOP K value and hydrogen content of the feedstock result in the
higher crackability，and hence the higher light olefin yields. Some representative feedstocks
and their olefin yields under DCC-I and DCC-II are shown in Table 2 and Table3,
respectively.
Table 2 DCC-Ⅰlight olefin yields from representative feedstocks
Number 1 2 3 4
VGO VGO+Resid VGO+ DAO VGO
Feedstock
Paraffinic base Paraffinic base Interm. base Naphthenic base
Density, g/cm3 0.8449 0.8621 0.9085 0.9249
UOP K 12.7 12.6 12.0 11.4
Hydrogen, t% 14.23 13.62 12.52 12.24
Olefin yield, wt%
Ethylene 5.8 3.6 3.5 3.6
Propylene 23.7 22.9 18.3 13.2
Butylenes 17.8 17.4 14.0 10.6

Table3 DCC-Ⅱlight olefin yields from representative feedstocks

Number 1 2 3 4
VGO VGO+Resid VGO+ DAO VGO
Feedstock
Paraffinic base Paraffinic base Interm. base Naphthenic base
Density, g/cm3 0.8579 0.8938 0.8983 0.9249
UOP K 12.4 12.5 12.0 11.4
Hydrogen, wt% 13.45 12.89 12.63 12.24
Olefin yield, wt%
Propylene 14.3 11.8 12.5 7.9

Isobutylene 6.1 5.3 4.6 3.5

Isoamylenes 6.8 5.5 5.8 4.1

Safety and Environmental

The DCCU emissions of waste water, waste gas, waste residue, powder and noise are similar
to that of the conventional FCC, so the measures and equipments of relative environmental
protection are similar for both DCC and FCC.
Catalysts

A series of DCC catalysts for different DCC types and feedstocks listed in Table 4 was
formulated and commercially available. MMC, the new generation DCC catalyst, has been
put into stream on several commercial DCCU, and resulted in both higher propylene
selectivity and higher propylene yield than the former ones. Table 5 lists the properties of
MMC catalyst.
 Table 4 DCC catalysts
DCC Commercializati
Designation Features
Type on Date
CHP-1 I 1990, 11 High bulk density, high propylene selectivity
CHP-2 I 1992, 9 Medium bulk density, high propylene selectivity
CRP-1 I 1994, 6 High hydrothermal stability
CRP-S I 1995, 5 Less active for fresh catalyst startup
CIP-1 II 1994, 6 Higher activity and bottoms crackability
Higher activity and bottoms crackability, metal
CIP-2 II 1998, 9
tolerance
Higher bottoms crackability, high propylene
CIP-3 I&II 1998, 10
selectivity
CIP-S II 1998, 9 Less active for fresh catalyst startup, metal tolerance
Higher activity and bottoms crackability, higher
MMC-1 II 2002, 11
propylene selectivity
MMC-2 I 2002, 9 higher propylene selectivity
Table 5 MMC catalysts
Items MMC-1 MMC-2
Pore volume, ml/g 0.29 0.28
2
Specific area, m /g 230 204
ABD，g/ml 0.76 0.79
o o
Cracking Index (520 C Reaction ，800 C/4h aged) ，wt% 72 76
AI，wt%/h 1.6 1.5
PSD
0-40 μm， v% 15.6 15.8
0-149 μm， v% 92.2 90.5
APS，μm 75.6 75.6

Economics

In order to evaluate and quantify the petrochemical opportunities opened to refiners，a linear program
model of a typical US Gulf Coast refinery was established using Haverly Systems GRTMPS. The base
case is a typical transportation fuels operation. Case Ⅱ utilizes the base case configuration，but opens
petrochemical options and lets the model decide the most profitable mix of products. Case Ⅲ allows the
same petrochemical opportunities，but the FCC has been replaced with a DCC maximum propylene
operation. The base model for this study includes typical process units consistent with the average of all
Gulf Coast refineries. The capacities of the individual process units are based on a 100,000 BPCD crude
unit.
The evaluation results of the model are listed in Table 6. There are significant differences between the
Case Ⅱ and Case Ⅲ. The propylene and para-xylene productions increase by 182.7% and 15.0%
respectively in the Case Ⅲ, however, the premium and regular gasoline productions reduce by 4.5% and
4.9% respectively. The economic analysis shows that Case Ⅲ has a US$94,129 per calendar day
advantage when the gross incomes are compared based on the productions shown in Table 6.
Table 6 Case comparison
Case Base case Case Ⅱ Case Ⅲ Case Ⅲ / Case Ⅱ
Products (BPCD)
Propane 4,755 6,005 7,334 +22.1%
Butane 2,785 3,801 3,780 -0.5%
Premium unleaded 17,507 2,330 2,225 -4.5%
Regular unleaded 36,159 45,014 42,811 -4.9%
Jet fuel 27,611 14,710 13,643, -7.3%
Diesel 8,190 17,031 12,188 -28.4%
Fuel oil 137 779 - -

Ethylene (TPA) - 61320 66,065 +7.7%

Propylene (TPA) 113,515 124,100 350,800 +182.7%
Benzene (TPA) - 63,500 73,300 +15.4%
Paraxylene (TPA) - 99,300 114,200 +15.0%
Butadiene (TPA) - 1,825 1,825 -

Commercial Experience

The first commercial DCC unit was put into production in 1990, and nine DCC units have been licensed
with a total capacity of 3.58MMTA, and the biggest one among them is 800KMTA. A 4.50MMTA DCC
unit for maximizing propylene production will be constructed and put into production in 2008.

Technological Services

Turn-key project or process design package can be submitted as well as technical consultant, training and
on-site service for start-up.