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General
situation
FRIPP
has been involved itself in the development of residue
hydrotreating technology since 1980s and had successfully
developed S-RHT whole set technology, FZC-XX series
catalysts for vaccum residue (VR) hydrotreating and
FZC-XXX series catalysts for atmospheric residue (AR)
hydrotreating. All these provide most effective solutions
for refiners to process and utilize heavy residue
reasonably. Up to now, FRIPP’s VR hydrotreating
catalysts and AR hydrotreating catalysts as well as S-RHT
technology had been well served the relevant units of
Shengli Refinery, Maoming Petrochemical Company (S-RHT
unit) and Dalian West Pacific Refining Co. Ltd. and
achieved successful run. The capacities of these units are
added up to 5.5 Mt/a, which has brought a great amount of
economic and social benefits.
Catalysts
Coping
with the reactions of residue hydrotreating process, FRIPP
successfully developed two series, four category
catalysts: guard catalysts, hydrodemetallization (HDM)
catalysts, hydrodesulphurization (HDS) catalysts and
hydrodenitrogenation (HDN) catalysts in which FZC-XX
series are specified for VR hydrotreating and FZC-XXX
series are specified for AR hydrotreating.
Characteristics
and functions of FZC-XX series catalysts
|
Category |
Catalysts |
Characteristics |
Functions |
|
Guard catalyst
|
FZC-1X series
|
Large
pore volume and big pore size |
Remove
Ni, V, Ca and impurities, protect post-catalysts from
coking and decelerate bed-pressure drop going up
quickly. |
|
HDM |
FZC-2X
series |
Large
pore volume and big pore size |
Maximally
remove nickel and vanadium |
|
HDS |
FZC-3X
series |
Stronger
acidity, smaller pore size, bigger surface area |
HDS,
HDN |
|
HDN |
FZC-4X
series |
Strongest
acidity, small pore, biggest surface area, high metal
content |
High
HDN activity, hydroconversion |
FZC-XX
series include four categories, sixteen catalysts, which
had been successfully commerciallized in Qilu
Petrochemical Company in 1995 and Maoming Petrochemical
Company S-RHT unit in 1999.
FZC-XXX
series include three categories (HDM, HDS and guard
catalysts) five catalysts, which had been successfully
commerciallized in Dalian West Pacific Refining Co. Ltd.
in November 1999.
Characteristics
and functions of FZC-XXX series catalysts
|
Category |
Catalysts |
Characteristics |
Functions |
|
Guard
cat. |
FZC-100 |
High
void rate |
HDM,
remove impurities, protect post-catalysts from coking
and decelerate bed-pressure drop going up quickly |
|
|
FZC-101 |
|
|
FZC-102 |
|
|
FZC-103 |
|
HDM |
FZC-201 |
High
pore volume and big pore size and larger void |
Maximally
remove nickel and vanadium |
|
HDS |
FZC-301 |
Smaller
pore size, bigger surface area and larger void |
High
HDS activity, hydroconversion |
Commercial
S-RHT unit
A
2.0MT/a S-RHT unit loaded with FZC-XX series catalysts was
designed and constructed in Maoming Petrochemical Company
in recent years. The unit was aiming at pretreating VR and
providing feed for RFCC.
Feedstock,
operating conditions and impurity removals
|
Feedstock |
|
|
Density，（20℃）kg/m3 |
976.9 |
|
viscosity，（100℃）mm2/s |
94.57 |
|
S，m% |
3.52 |
|
N,
m% |
0.26 |
|
CCR,
m% |
12.64 |
|
Ni+V,
μg/g |
84.0 |
|
Operating
conditions |
|
|
run
time，hr |
5800 |
|
reaction
temperature,℃ |
380 |
|
hydrogen
partial pressure，Mpa |
15.3 |
|
LHSV,
h-1 |
0.20 |
|
gas/oil
ratio of first reactor（v/v） |
800 |
|
Impurity
removals |
|
|
HDS，% |
90.86 |
|
HDN，% |
66.58 |
|
HDCCR，% |
65.58 |
|
HDM（Ni+V），% |
87.48 |
Properties
of main products
|
Naphtha |
|
|
S，μg/g |
15 |
|
N，μg/g |
2 |
|
Boiling
range，℃ |
43~159 |
|
Diesel
oil |
|
|
S，μg/g |
250 |
|
N，μg/g |
120 |
|
Boiling
range，℃ |
197~361 |
|
Cetane
number |
48 |
|
Hydrotreated
AR |
|
|
Density,
(20℃), kg/m3 |
938.1 |
|
S，m% |
0.37 |
|
N,
m% |
0.10 |
|
CCR,
m% |
5.00 |
|
Ni+
V, μg/g |
12.1 |
The
data show that the impurities such as sulphur, nitrogen
and metal in residue have been effectively removed in
Maoming S-RHT unit. The unit contributes not only small
amount of naphtha and some high quality light diesel oil
with low sulphur, but also about 90% yield of hydrotreated
atmospheric residue that is qualified RFCC feedstock.
Therefore, S-RHT combined with RFCC has effectively
achieved full conversion of sour residue.
Commercial
atmospheric residue hydrotreating unit
FZC-XXX
series catalysts were put into commercial application in
Dalian West Pacific Refining Co. Ltd. ARDS unit in
November 1999. The unit has A and B two trains of
reactors. A train was loaded with imported catalysts and B
train with catalysts developed by FRIPP.
Feedstock
|
density，（20℃）kg/m3 |
955.1 |
|
viscosity，（100℃）mm2/s |
24.95 |
|
S，m% |
2.91 |
|
N,
m% |
0.18 |
|
CCR,
m% |
8.19 |
|
Ni+V,
μg/g |
37.21 |
Properties of hydrotreated AR and impurities removal
|
Run
time，hr |
7200 |
|
Train |
A |
B |
|
Catalyst |
from
other provider |
FZC-XXX
series |
|
AR
properties |
|
|
|
density,
(20℃)kg/m3 |
0.9219 |
0.9158 |
|
S，m% |
0.45 |
0.33 |
|
N,
μg/g |
1307 |
1098 |
|
CCR,
m% |
4.29 |
3.73 |
|
Ni+
V, μg/g |
12.39 |
12.40 |
|
Impurity
removal |
|
|
|
HDS，% |
87.2 |
96.0 |
|
HDN，% |
40.3 |
49.6 |
|
HDCCR，% |
56.7 |
62.4 |
|
HDM（Ni+V），% |
72.5 |
72.48 |
The
data show that the HDS, HDN and HDCCR activities of
FZC-XXX series catalysts are better than that of the
imported one and the HDM activity of the two trains are
almost the same.
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