TECHNICAL PAPER

A New Residual Desulfurization Process*

by Jun-ichi Kubo**, Yutaka Oguchi*** and Hirotsugu Nomura***

Summary: A new residual desulfurizationprocess using a new type reactor and catalyst
had been developedextendingover 6 years as a part of the National Researchand Development
Program. We have taken over the developmentwork comprising catalyst improvementand
500 BPSD test plant operationsfor vacuum residuesand it is planning to constructa 10,000
BPSD test plant.

tween them can be listed up as indicated in

1 Introduction Table 1, but the fundamental differences are as
Sulfur removal from fuel oils has become a follows. In case of type (1), it is impossible to
social demand and direct desulfurization tech- replace the catalyst on operation, and therefore
niques of fuel oils were taken up as a National the feed rate (i. e. space velocity) is restricted
Research and Development Program in 1967 by in case where the catalyst deactivation is
Ministry of International Trade and Industry of conspicuous or the pressure drop increase is
Japan. notable because a scheduled duration of run
We joined in the project in 1967 and our de- length should be secured. Moreover, the reac-
velopment work had been carried out by three tion temperatures are different between the
steps scale-up (0.5 BPSD, 10 BPSD, and 500 start-of-run and the end-of-run because the
BPSD) extending over six years aiming a new catalyst deactivation is covered up by raising the
desulfurization process with a new type reactor temperature. Process design must be fulfilled
and catalyst. Afterwards, we have taken over the at the most severe condition; end of run and
development work comprising catalyst improve accordingly the desulfurization unit and its inci-
ment and 500 BPSD test plant operations, more- dental plants can not be made good use of. How-
over, we are now planning to construct a 10,000 ever, the process constitution is rather simple
BPSD test plant. comparing with type (2).
We would like to give an outline of the process On the contrary, in type (2), it is possible to
characteristics and the experimental works in this replace the catalyst on operation, so the feed
paper. rate restriction owing to the catalyst life can be
2 Process Description eliminated and the operating conditions can be
maintained constant during the whole run.
2.1 Characteristics of the Process with
Therefore, the desulfurization unit and its inci-
Fluidized Catalyst
dental plants can be designed efficiently but the
Several direct desulfurization plants are on
operation in the world and they have individual process must be complicated and has some diffi-
culties in engineering aspects.
characteristics in their catalysts and process con-
2.2 Reactor Description
stitutions. However, they can be diyjded into
A sketch of the reactor used in this process is
two groups, namely (1) fixed bed type (2)
indicated in Fig. 1. Oil and hydrogen con-
fluidized catalyst type. Most of the proposed
taining gas are introduced from the bottom of it.
processes belong to the former one, but the The catalyst is fluidized by the oil and gas in the
fluidized catalyst is used in our process. The
inner tube and goes upwardly. At the upper
features of both types are summarized in Table 1
edge of the inner tube, the oil linear velocity
conforming to our development work and ex-
decreases suddenly and the catalyst settles down
periences. A great number of differences be-
into the outer space. At the outer space, the
* Received Octover 7
, 1974.
** Planning and Process Technology Section , Nippon catalyst forms accumulated layer and it moves
Oil Co., Ltd. (1-3-12, Nishi-shinbashi, Minato-ku, downwardly. At the steady state, the amount
Tokyo 105).
*** Central Technical Research Laboratory of catalyst overflowing from the inner tube to the
, Nippon Oil
Co., Ltd. outer spase is balanced with the catalyst sliding

Bulletin of The Japan Petroleum Institute

 Kubo, Oguchi and Nomura: A New Residual Desulfurization Process 101

Table 1 Characteristics of Fluidized Catalyst Type Processes

stantially, and the catalyst settles down by gravity

and forms accumulated layer by appropriate
sizing of inner tube. We have never encountered
the plugging or coking of catalyst because the
catalyst always moves downwardly at the outer
space. We can say with the experimental results
with three scales of reactors that the catalyst
is not deactivated at the outer space because
substantial chemical reactions do not take place.
The merits of the reactor can be concluded
as follows:

(1) Catalyst entrainment is prevented. Ac-

cordingly, relatively small particles of catalyst
can be used.
(2) The amount of recycle oil can be reduced.
(3) Larger surface area of catalyst is used
Fig. 1 Reactor Sketch
for chemical reactions and higher reaction rate
can be expected.
from the outer space to the inner tube then the
(4) Particulate fluidization can be obtained.
catalyst recycles from the inner tube to the outer
(5) More flexible operation can be expected
space. because the upper level of catalyst bed is always
Oil and gas flow up only in the inner tube in controlled by the upper edge of the inner tube
connection with the particular pressure balance regradless of fluctuation of flow rate
caused by the constituent of the reactor and (6) Deactivated catalyst can be withdrawn
therefore, chemical reactions substantially take place selectively from the lower part of the inner tube
only in the inner tube. The catalyst entrainment because of the double tube constituent and cata-
preventer taking advantage of the double tube lyst consumption can be reduced.
constituent is equipped in a reactor. Vapor and (7) Errosion problems at the inner face of
liquid are separated at the upper part of the reactor shell need not be considered.
reactor.
(8) Relatively small spheres of catalyst (aver-
At the outer space, liquid does not flow sub- age diameter 1mmφ) are employed, so catalyst

Volume 17, No. 1, April 1975

102 Kubo, Oguchi and Nomura: A New

Fig. 2 500 BPSD Test Plant Process Flow Scheme

handlings such as transportation, addition and of non-selective withdrawal.

withdrawal are easy. Catalyst defacement and We have established a particular catalyst
crushing can be prevented remarkably. addition and withdrawal system to and from
However, the demerits of the reactor are as reactors.
follows: 2.4 Process Flow
(1) Desulfurization do not occur at the outer A simplified process flow scheme is shown in
space, so some part of reactors is wasted from Fig. 2. Charge oil mixed with hydrogen con-
reaction volume viewpoint. taining gas en route to the heater is heated up
(2) Constitution of reactor internals is com- by the heater and fed to the first reactor. Oils
plicated and some techniques are required to and gases are separated at the top of the reactors
get desirable fluidization and circulation of and oils are recycled to the reactors to get cata-
catalyst in reactors. lyst fluidized. Oil product from first reactor is
2.3 Catalyst Replacement fed to the second reactor and it is desulfurized
Catalyst activity is maintained constant by to the aimed sulfur level. After eliminating
replacing the catalyst in this process. Provided dissolved gas at several stages of pressures, the
that the sulfur content in product is fixed, oil product is sent to the fractionator section.
when the catalyst activity is taken with high Make-up hydrogen is compressed and mixed
replacing rate of catalyst, operating conditions to the recycle gas and it is charged to the re-
can be made mild, that is, lower reaction tem- actors respectively with the charge oils. Reactor
perature or higher space velocity can be em- effluent gas separated from the oils at the top

ployed, however, catalyst consumption becomes of the reactors are cooled and condensed of its
high. On the contrary, when the catalyst con- light hydrocarbons, and it is washed by amine
sumption is reduced, the catalyst activity is low solution to absorb hydrogen sulfide. The greater
and severe operating conditions are necessary. part of the hydrogen-sulfide free gas is recycled
The selection of catalyst activity should be deter- to the reactors by recycle gas compressor, but
mined by an economical optimization. some part of the gas is fled to secure the hydrogen
Anyway, reaction temperature does not have purity of recycle gas.
to be raised up according to the catalyst de-
3 Outline of the Experimental Works
activation as is the case with fixed bed, and the
operating conditions are constant in steady 3.1 Development Procedure
operation. The process has been tested on three different
The deactivated catalyst can be selectively scales;
withdrawn in this type of reactors, and the (1) 0.5 BPSD (2) 10 BPSD (3) 500 BPSD
catalyst consumption is reduced to about 60% Prior to the desulfurization runs on each step,

Bulletin of The Japan Petroleum Institute

Residual Desulfurization Process 103

Fig. 3 One of the 500 BPSD Runs (Khafji Atmospheric Residue)

and vacuum residues but we would like to refer

to the previous operations in this paper.
One of the runs treating Khafji atmospheric
residue is illustrated in Fig. 3. Catalyst in
reactors was replaced on operation to recover the
catalyst activities in reactors.
Main substantial facts and information obtained
in these tests are illustrated in the following
paragraphs.
3.2.1 Temperature Profiles in Reactor
Examples of temperature profiles in reactors
are shown in Fig. 4. Very uniform temperature
Fig. 4 Reactor Temperature Profiles distributions were obtained because the catalyst
was fluidized. Quenching of reaction zone was
individual model test units were built and catalyst not necessary at all in any case.
behavior was investigated by them. These 3.2.2 Catalyst Movement in Reactor
model tests of reactors were effective in sizing The level detector using γ-ray was equipped to
of reactor internals and deciding of operating see the catalyst movcments. Fluidization and

conditions referring to the catalyst movement. circulation of the catalyst were very preferable

Micro-reactors of fixed bed type have been during the operations.

used not only to test the catalyst but to obtain 3.2.3 Catalyst Entrainment
the basic process information such as charge oil Catalyst entrainment with oil is the most
properties, operating conditions, product pro- troublesome matter in using fluidized catalyst.
perties and catalyst deactivations. Devices to prevent the catalyst carry-over making
3.2 500 BPSD Test Plant Operations use of double tube constitution were installed
Tests by 500 BPSD test plant were carried in the reactors, and they were effective to reduce
out for total 3,500 hours treating Khafji and the catalyst carried over despite that relatively
Arabian Light atmospheric residues. After- small sized catalyst (1mm average diameter)
wards, we enforced a remarkable repair of the plant was used. Figure 5 shows the amount of the
and it is now on operation to make attempts of catalyst carried over on operation. Small amount
severe desulfurization of atmospheric residues of fine catalyst and crushed catalyst are included
Volumc 17, No, 1, April 1975
104 Kubo, Oguchi and Nomura: A New

Fig. 7 Pressure Effect on Reaction Rate

Fig. 5 Catalyst Entrainment of 500 BPSD Test Run

Table 2 Material Balance of Khafji Atmospheric

Residue Treating(S=3.83→1.00%)

Fig. 6 Temperature Effect on Reaction Rate

in the charged one, so carry-over can be found

Table 3 Material Balance of Arabian Light Atmos-
immediately after the start of run and catalyst
pheric Residue Treating(S=2.88→0.64%)
additions to reactors, but after those, there is no
catalyst entrained. Catalyst carried with liquid
was caught by cyclones.
3.2.4 Catalyst Addition and Withdrawal
Catalyst addition and withdrawal were tested
for fifteen times during the runs and they
were accomplished without troubles. It is
understood by Fig. 3 that the catalyst activity
in a reactor can be recovered by the replacement.
It was confirmed by the activity tests that the
deactivated catalyst was selectively withdrawn.

4 Discussions of Experimental Data

A great number of experimental works have

been done and experimental data have been 21 kcal/mol.
obtained therewith, but we would briefly make 4.2 Hydrogen Pressure Effect on Desulfuri-
mention of the conclusions to explain the process zation
characteristics in this paper. Following de- Hydrogen pressure effect on rate of desulfuri-
scriptions are based on the Khafji and Arabian zation is indicated in Fig. 7. The relation in
Light atmospheric residue treating and the sulfur Fig. 7 shows that it is applicable regardless of the
contents of product oils are higher than 1.0wt% scale of reactors. Pressure effect on desulfuri-
and 0.6wt% respectively. zation is considerably different from the fixed
4.1 Temperature Effect on Desulfurization beds. It would be the reason that the state of
Temperature effect on pseudo second order liquid and gas in reactors is quite different from
reaction rate of desulfurization is shown in Fig. that of fixed beds.
6. Activation energy is calculated to be about 4.3 Material Balance

$ulletin of The Japan Petroleum Institute

Residual Desulfurization Process 105

Table 4 Feed and Product Properties(500 BPSD)

Fig. 8 Hydrogen Consumption

Fig. 10 Scale Effect on Desulfurization

change by reactor scale so much and most of them

are identified by sulfur content.
4.7 Scale Effects on Desulfurization Process
As previously mentioned, there exist problems
accompanying the scale-up of reactors as follows:
(1) Catalyst movement problems
Fig. 9 Light Hydrocarbon Formations with Sulfur
Conversion
(2) Chemical reaction problems
Referring to the former ones, catalyst move-
The material balances of Khafji and Arabian ment is somewhat differed with reactor scale,
Light atmospheric residues to reduce the sulfur so it was judged to be impossible to fully estimate
contents to 1.0wt% and O,6wt% respectively the catalyst movement in larger reactors from the
are shown in Table 2 and Table 3. data obtained with smaller ones. Therefore, model
4.4 Hydrogen Consumption tests of reactors were carried out at individual
Figure 8 shows the relation between sulfur step. However, relating to the latter ones,
conversion and hydrogen consumption by 0.5 reaction rate, hydrogen consumption, process
BPSD and 500 BPSD runs. These data coincide
yields, light hydrocarbon formations and product
considerably with each other.
properties and also their changes with operating
4.5 Light Hydrocarbon Formations conditions are not differed with reactor scale so
The amount of light hydrocarbons formed is much. For example, rate of desulfurization
mainly related to the sulfur conversion and and temperature effect on it in 500 BPSD reactor
reaction temperature.Fagure 9 shows the rela- are essentially same as those in 0.5 BPSD reactor
tion between light hydrocarbon formations and
as shown in Fig. 10. Therefore, it would be
sulfur conversion at 400℃. Light hydrocarbon
possible to estimate those of larger scales by the
formations are also increased with reaction results with the smaller ones without substantial
temperature. errors.
4.6 Product Properties 4.8 Catalyst Consumption
Examples of feed and product properties are The most important characteristics of this
shown in Table 4. Product properties do not process is catalyst replacement on operation and

Volume 17, No. 1, April 1975

106 Kubo, Oguchi and Nomura: A New

Fig. 13 Arabian Light Atmospheric Residue Desul-

Fig.11 LHSV-Temperature-Throughput pcr Cata- furization by 500 BPSD Test Plant with
lyst Relations of Khafji Atmospheric Residue
Improved Catalyst
(Sulfur 3.80→1.20%)

Fig.12 LHSV-Temperature-Throughput per Cata-

lyst Relations of Arabian Light Atmospheric Fig. 14 Arabian Light Vacuum Residue Desulfuri-
Residue (Sulfur 2.88→0.7%) zation

so catalyst consumption is one of the essential

process variables. Figure 11 and 12 illustrate the
relations between the basic operating conditions
and catalyst consumption when Khafji and
Arabian Light atmospheric residues are reduced
of their sulfur contents to 1.2% and 0.7% re-
spectively, based on the 500 BPSD runs.
5 Catalyst Improvement

After the runs previously mentioned, the

catalyst perfcrmancc was remarkably improved.

And now severe desulfurization of atmospheric

residues (sulfur in product is 0.1∼0.3%) and

Fig. 15 Arabian Medium Vacuum Residue Desulfuri-
vacuum residues are being tested by 500 BPSD zation
test plant and considerably excellent results have
are estimated with various vacuum residues and
been obtained. One of the runs with Arabian
they are illustrated in Fig. 14, 15, 16. Maximum
light atmospheric residue is illustrated in Fig.13.
space velocities and throughputs per catalyst are
6 Process Estimation for Vacuum Residues also shown in Fig. 14, 15, 16, provided that the
by the Improved Catalyst
same catalyst is used in fixed bed to take the
The correlations of sulfur content in product continuous run length 8,000 hours.
with space velocity and throughput per catalyst In desulfurization of vacuum residues the

Bulletin of The Japan Petroleum Institute

 Residual Desulfurization Process 107

Fig. 16 Arabian Heavy Vacuum Residue Desulfuri- Fig. 17 Cost with Sulfur in Product by Fixed Bed
zation Process and This Process

catalyst deactivations are remarkable, so the Dr. Tadao Shiba, the professor emeritus of
space velocities have to be lowered to secure a Tokyo Institute of Technology, and members of
certain period of run length in fixed bed. How- Agency of Industrial Science and Technology and
ever, space velocity restriction can be removed National Chemical Laboratory for Industry.
by the catalyst replacement in this process and The 500 BPSD test plant was designed and
then relatively high space velocities can be constructed in co-operation with Chiyoda Chemi-
employed. The reason why the catalyst con- cal Engineering & Construction Co., Ltd. and
sumptions are comparatively low is that the Niigata Engineering Co., Ltd.
deactivated catalyst is selectively withdrawn.
References
The trends previously mentioned can be
1) Kaiser, F. J. et al., Proc. API, Div. Refining, 473
economically explained by Fig. 17. The relative
(1973).
cost to the base with sulfur level in product of 2) Watkins, C. H. et al., ibid., 498 (1973).
Arabian Light atmospheric and vacuum residues 3) Van Driesen, R. P. et al., NPRA Annual Meeting,
AM-73-35 (1973).
are indicated in Fig. 17 in which the base is taken 4) Steele, D. M. et al., 38th Midyear Meeting of API,
that Arabian Light vacuum residue is reduced Division of Refining, Preprint No. 40-73 (1973).
5) Herman Tayler, ibid., Preprint No. 41-73 (1973).
of its sulfur to 0.7%.
6) Mosby, J. F. et al., Proc. API, Div. Refining, 488
Acknowledgement (1973).

The development works had been guided by

Volume 17, No. 1, April 1975