a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r. c o m / l o c a t e / c h n j c
Review
A R T I C L E I N F O
Article history:
Received 20 November 2012
Accepted 30 December 2012
Published 20 January 2013
Keywords:
Residue
Asphaltenes
Gasoline
Diesel
Catalytic hydrogenation
Fluid catalytic cracking
Propylene
A B S T R A C T
The primary tasks of refineries in the future are to improve the yield of light oil and to produce
clean fuels and highquality chemical raw materials. The efficient conversion of heavy oil is neces
sary to improve the yield of light oil. This conversion requires some crucial technologies, including:
(1) residue hydrotreating technology, (2) the research institute of petroleum processings (RIPPs)
integrated combination process for residue hydroprocessing, (3) the integration of selective hydro
genation of fluid catalytic cracking gas oil with selective catalytic cracking process, and (4) the com
bination of superficial solvent deasphalting, hydrotreatment of deasphalted oil, and fluid catalytic
cracking technology. The most important technologies for producing clean fuels such as qualified
gasoline and diesel include the RIPPs selective hydrodesulfurization technology, the RIPPs hydro
genation technology for producing ultralowsulfur diesel fuel, and catalysts for producing RS1000
and RS2000 (grades of ultralowsulfur diesel). To produce high quality chemical raw materials,
the Sinopec hydroprocessing for maximum propylene of fluid catalytic cracking process is of vital
importance. The characteristics and effects of these technologies are summarized in this article.
2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
An increasing proportion of heavy and sour (highsulfur)
crude oil is being processed globally, resulting in deteriorating
crude oil quality. In 1996, sour and highsulfur crudes repre
sented 57% and heavy crudes represented 11.1% of total glob
al oil production, whereas in 2010 these proportions grew to
75.0% for sour and highsulfur crudes and 15.6% for heavy
crudes. Based on an analysis of available crude resources, re
fineries of all countries, including China, will continue pro
cessing a growing amount of inferior crude oil in the future.
Increasingly stringent environmental regulations are accel
erating improvements in petroleum product quality in China.
Beginning March 1, 2008, the Beijing metropolitan area began
enforcing the national IV emission standard, which was equiv
alent to the Euro IV standard and specified a 50 g/g limit for
vice life of the RHT series catalysts was extended by 22% [1].
Afterwards, the Chinese Petroleum Corporation, Taiwan, upon
applying the RHT series catalysts, was able to run the residual
hydrotreating unit for 10 months, which was 3 months longer
than that achieved by similar overseas reference catalysts, and
the service life of the RHT series catalysts was extended by
more than 40%. This resulted in significant economic benefits
for the company.
Since the RHT series residual hydrotreating catalysts were
first applied in commercial scale on the upflow reac
tor/residual desulfurization unit at the Qilu Petrochemical
Branch Company in October 2002, there have been 16 suc
cessful commercial applications of these catalysts in 16 process
units coupled with 4 other units under construction that plan to
adopt the RHT technology.
2.1.2. Residue hydrotreating integrated with catalytic cracking
process
The traditional residue hydrotreatingFCC combination
technology processes hydrotreated tail oil in the FCC unit with
the FCC heavy cycle oil (HCO) circulating inside the unit, repre
senting a onedirectional process scheme. Since the HCO con
tains a large amount of polynuclear aromatic hydrocarbons,
recycling of this oil would lead to reduced light oil yield and
increased coke and gas yields. If the hydrotreating unit runs on
pure VR, it could not operate for long because of the extremely
high viscosity of VR. However, if the unit runs on AR or on VR
that is blended with vacuum gas oil (VGO), serving as a diluting
oil, there would be insufficient supply of feedstock to the hy
drotreating unit. In this case, the goal of maximizing high qual
ity middle distillate oil could not be achieved.
Rather than circulating HCO inside the FCC unit, the RICP
technology mixes this heavy cycle oil with VR to serve as part of
the feedstock to the hydrotreating unit. With this technology,
the hydrotreated product is routed back to the FCC unit for
further processing so that the HCO can circulate along a large
loop in the hydrotreating and FCC units, as shown in Fig. 1.
Commercial operation of the RICP process at the Qilu Petro
chemical Branch Company has demonstrated that the RICP
technology has obvious advantages to both the residue hy
drotreating unit and the FCC unit, resulting in remarkable eco
nomic benefits for the refinery [2,3].
H2
VR
resid HT
in fixed
bed
gas
offgas
naphtha
LPG
diesel
FCC naphtha
RFCC
FCC diesel
VGO
>350 oC
hydrotreated resid
HCO
slurry
Technology
Reference case
RICP
Difference
Off gas
2.14
2.02
0.12
LPG
13.53
13.40
0.13
Slurry
3.54
2.45
1.09
Coke
8.66
8.09
0.56
Off gas
Coke
Selectivity (%)
5
offgas
4
3
VRDS
feedstock
1
0
10
20
30
40 50 60 70
Conversion (%)
80
LPG
H
S
C
C
90 100
Fig. 2. Relationship between the yield of offgas and coke and the con
version rate [4].
FGO
M
I
P
H
A
R
gasoline
diesel
slurry
hydrotreated
FGO
Table 2
Differences between the pilot scale experimental results of IHCC and
FCC.
Technology type
Catalyst
Feed stock
Density
Carbon residue
Hydrogen content
Product distribution (%)
Dry gas
Liquefied gas
Gasoline
Diesel oil
Heavy oil
Coke
Light oil yield
Total liquid yield
IHCC
Specialized catalyst
JingMen mixed
residuum
0.9285
4.9
12.2
3.28
16.16
45.38
25.47
1.27
7.85
70.85
87.01
FCC
MLC500
JingMen mixed
residuum
0.9285
4.9
12.2
3.63
18.53
38.31
21.02
6.89
11.44
59.33
77.86
bons formed in the process.
3. The hydrotreated FGO, which can serve as the feedstock
for operations such as the HSCC, FCC, and maximizing
isoparaffin (MIP) processes, is again subjected to catalytic
cracking using the appropriate catalyst and process regime.
This results in selective cracking of the alkane structural
groups while retaining aromatic structural groups that can be
treated by hydrosaturation of PNAs using the HAR process,
thereby forming naphthenic hydrocarbons or monocyclic aro
matics.
Thus, it is evident that on the feed oil molecular level, IHCC
technology can enhance the coordination and integration of
existing refining technologies. Pilot scale IHCC and FCC pro
cesses have demonstrated that the adoption of the IHCC pro
cess has resulted in apparently increased light oil and total
liquid yields with significant reduction in coke yield, as shown
in Table 2.
2.1.4. Superficial solvent deasphaltingDAO hydrotreatingFCC
technology
Some grades of VR derived from imported sour crudes con
tain high nickel and vanadium contents and cannot be pro
cessed directly with the fixedbed residue hydrotreating tech
nology. An urgent issue concerns how to achieve in an eco
nomic and effective manner a maximum yield of clean automo
tive fuel from lowvalued VR having a high sulfur and heavy
Heavy solvent (C4 and C5)
VR
(100%)
S
D
A
DAO
(80% 90%)
Hard pitch
(10%20%)
Furnace
-Vapour
-Energy
Medium-pressure
Gas
D
A
O
H
T
Naphtha
Diesel oil
H-DAO
Gas
F
C
C
LPG
Gasoline
LCO
HCO
Oil slurry
metals content.
The superficial solvent deasphaltingDAO hydrotreat
ingFCC technology (SHF) developed by the RIPP is an effective
means for processing inferior residuum with a high content of
sulfur and heavy metals. Using heavy solvents (butane and
pentane), the SHF technology can remove almost all asphal
tenes and more than 70% of heavy metals from inferior vacu
um residue while providing a high yield of deasphalted oil
(DAO) in the range of 80%90% [3]. The hydrotreated DAO is a
premium FCC feedstock that can be used to manufacture clean
gasoline with low sulfur and olefins contents. A schematic flow
diagram of the SHF process is presented in Fig. 4.
The results of deasphalting of VR derived from Arabian light
(AL) crude using normal pentane as the solvent are presented
in Table 3. While the mass fraction of asphaltenes in DAO was
reduced to less than 0.05% and the nickel and vanadium con
tents were also significantly reduced, the DAO yield reached
85.5%.
The DAO was then subjected to pilotscale hydrotreating
tests, resulting in the product distributions and properties
presented in Tables 4 and 5, respectively.
The density, viscosity, and Conradson carbon residue (CCR)
values of hydrotreated DAO were apparently improved along
with a remarkable reduction in sulfur, nitrogen, and metals
contents. As a result, this hydrotreated DAO can serve as a
premium FCC feedstock. The distributions and properties of
major products formed during catalytic cracking of tail oil ob
tained during hydrotreating of ALderived DAO are presented
in Tables 6 and 7, respectively.
The pilotscale catalytic cracking test of tail oil obtained
during hydrotreating of DAO derived from AL resulted in a total
yield of light hydrocarbons exceeding 83%, and the sulfur con
tent in FCC gasoline was low enough to meet the Euro III
Table 3
Pentane deasphalting of VR derived from Arabian light crude.
Vacuum residues
Deasphalt
of saudi arabian
Asphalt
ed oil
light crude oils
Yield (%)
100
85.5
14.5
Viscosity (100 C, mm2/s)
498.8
117.3
Conradson carbon residue (%)
18.7
11.5
61.2
1.001
0.9715 1.150
Density (20 C, g/cm3)
S (%)
4.04
3.89
5.92
Ni (g/g)
20.5
3.4
127
V (g/g)
71.8
14.9
402
nHeptane insoluble (%)
6.8
<0.05
Softening point (R&B) (C)
155
Item
Table 4
Distributions of products obtained from pilotscale hydrotreating of
DAO derived from AL.
Products
Distribution
H2S + NH3
3.7
C1C4
0.5
C5180 C
1.0
180350 C
8.5
350 C+
87.4
Technological conditions: raw 100 and hydrogen 1.1 in gross of input
101.1, (RG10A/RG10B)/RDM1/RMS1 catalyst, p(H2) 8.0 MPa, LHSV
0.5 h1, reaction temperature 380 C, H2/Oil 650 V/V.
Density
Viscosity
Carbon
S (%)
(20 C, g/cm3) (100 C, mm2/s) residue (%)
0.9715
117.3
11.5
3.89
0.8800
< 200 g/g
0.9400
35
3.5
0.30
N (%)
Ni (g/g)
V (g/g)
250 g/g
0.13
3.4
<1
14.9
<1
Condensation
point (C)
18
Cetane
number
40
Table 7
Properties of products obtained during FCC of tail oil formed upon hydrotreating of DAO derived from AL.
Sulfur
Density
Alkene (%)
(g/g)
(20C, g/cm3)
FCC gasoline
0.7498
25
25
FCC diesel oil
0.9452
0.20
RONResearch octane number. MONMotor octane number.
Product
RON
MON
90.1
79.8
Condensation point
(C)
39
Real gum
(mg/100ml)
120
Table 8
Comparison of properties between pitch/water slurry fuel and other fuels [6].
Slurry
Hard pitchwater slurry
Coalwater slurry
Tar pitchwater slurry
Raw material
hard pitch
coal
tar pitch
Content (%)
69 1
70
72 1
Viscosity (cP 30 C)
1000
1000
<900
Density (g/cm3)
1.1
1.2
1.01
Table 6
Distributions of products obtained during FCC of tail oil formed upon
hydrotreating of DAO derived from AL.
Product
Dry gas
Liquefied gas
Stable gasoline
Light diesel oil
Slurry oil
Coke
Lose
Total
Total light hydrocarbon yield
Distribution (%)
3.9
12.8
45.0
25.5
5.0
7.3
0.5
100.0
83.3
Pitch
Fluidizer Dispersant
Stabilizer
Pitch
bunker
Slurry
making
Pitch/water
slurry tank
1.0
(1)
(2)
Intensity
(3)
(4)
(5)
30
40
50
60
70
0.8
0.6
0.4
0.2
0.0
4.5
(6)
20
1.2
CoMoO4
MoO3
80
2/( o )
Fig. 6. XRD patterns of oxidized catalysts [7]. (1) CoMoC/Support1;
(2) Support1; (3) CoMoC/Support2; (4) Support2; (5) Co
MoC/Support3; (6) Support3.
5.0
5.5
6.0
Slab length of (Co)MoS2
6.5
7.0
Fig. 7. Relationship between the size of the active phase and the selec
tivity of the hydrodesulfurization catalyst [7].
Table 9
Comparison of running results between RSDSI and RSDSII at the Shanghai Petrochemical plant.
Technology
S (g/g)
Olefin (%)
RSDSI technology
Feedstock
440
46.9
Products
36
35.3
RSDSII technology
Feedstock
470
40.8
Products
34
39.7
AKIAntiknock index (often written on pumps as (RON + MON)/2).
RON/MON
94.9/81.7
93/80.6
93.6/80.5
93.0/80.6
Loss of RON
1.9
0.6
Loss of AKI
1.2
0.3
100
S content (g/g)
80
60
40
20
0
50
100
150
200
Run time (d)
250
300
Table 10
Properties of feedstocks used for producing ULSD by the RTS technology.
Sulfur
Density
content
3
(20C, g/cm )
(%)
Zhenhai straightrun diesel
0.8388
0.78
Maoming straightrun diesel
0.8514
1.50
Iran straightrun diesel
0.8449
1.10
Feedstock
Nitrogen
Boiling range (ASTM D86, C)
Chroma (ASTM Cetane number
content
Initial boiling
Final boiling
D1500)
(ASTM D4737)
50% 90%
(g/g)
point
point
155
0.6
54.5
193
283 347
377
100
0.6
56.8
206
313 364
379
75
0.6
55.6
216
292 346
369
Table 11
Properties of ULSD produced by the RTS technology.
Feedstock
Total
P(H2)/ space
MPa velocity
(h1)
6.4
6.4
6.4
1.6
2.0
2.5
V(H2)/
V(oil)
300
300
300
Density Chroma
(20 C, (ASTM
g/cm3) D1500)
0.8162
0.8248
0.8188
0.1
0.1
0.1
Cetane
Sulfur Nitrogen number Initial boil
content content
index
ing point
(g/g) (g/g)
(ASTM
(50%)
D4737)
8.6
<0.5
60.2
169/271
9.5
<0.5
61.5
184/287
7.0
<0.5
60.5
174/278
Final boiling
point
(90%)
338/371
348/373
337/364
Table 13
Comparison of activity between the RS2000 and RS1000 catalysts.
Reaction temperature (C) Base line Base line+15
Product sulfur content, g/g
RS1000
148
16
RS2000
98
7.0
Product nitrogen content, g/g
RS1000
0.6
<0.2
RS2000
<0.2
<0.2
Relative HDS activity (%)
RS1000
100
100
RS2000
132
172
Feedstock conditions: p(H2) 6.4 MPa, LHSV 2.0 h1.
Base line+30
8.5
2.0
<0.2
<0.2
100
258
Graphical Abstract
Chin. J. Catal., 2013, 34: 4860 doi: 10.1016/S18722067(11)605081
Dry gas
Gas
H2
Resid
Resid
Hydro
treating
LPG
Naphtha
Diesel
Hydrotreated
bottom
FCC gasoline
FCC diesel
C
HCO
Slurry
[4]
[5]
3. Conclusions
The primary challenge facing the petroleum refining indus
try of China is the production of cleaner fuels and premium
chemical feedstocks. To increase light distillate oil yield, up
grade the quality of automotive fuels, and produce more chem
ical feedstocks, highefficiency catalysts should be tailored to
cope with the specific features of crude slates and petroleum
fractions. This is necessary to optimize the process regime and
to develop crucial technology packages so that the future re
[6]
[7]
[8]
[9]
[10]