Note: Descriptions are shown in the official language in which they were submitted.
'7~
PROCESS FOR TtlE PREPARATIO~ OF A HYDROCAP~BON MIXTURE
The invention relates to a process for the preparation of a
hydrocarbon mixture having a Ramsbottom Carbon Test value (RCT)
of a %w and an initial boiling point of TlC.
The RCT is an important parameter in the assessment of the
suitability of heavy hydrocarbon mixtures as feed stocks for
catalytic conversion processes, such as catalytic cracking,
carried out in the presence or absence of hydrogen~ for the
preparation of light hydrocarbon distillates, such as gasoline
and kerosine. According as the feed has a higher RCT~ the
catalyst will be deactivated more rapidly in these processes.
Residual hydrocarbon mixtures, such as residues obtained in
the distillation of a crude mineral oil and asphaltic bitumen
separated in the solvent deasphalting of the said distillation
residues or of residues obtained i.n the distillation of a
]5 hydrotreated residual fraction of a crude mineral oil generally
have to~ high an RCT to be suitable without previous treatment
for use as feeds for the above-mentioned catalytic conversion
processes. Since the RCT of residual hydrocarbon mixtures is
mainly determined by the percentage of asphaltenes present in
the mixtures, a reduction of the RCT of these mixtures can be
obtained by reducing the asphaltenes content. Basically, this
may be achieved in two ways. Part of the asphaltenes may be
separated from the mixture by solvent deasphalting, or part of
the asphaltenes may be converted by subjecting the mixture to a
catalytic hydrotreatment. For the reduction of the RCT of
distillation residues the latter method is preferred, in the
first place, because its yield of heavy product with a low RCT
is higher and further because, in contrast to the former method,
where asphaltic bitumen is obtained as a by-product, it yields a
valuable C5 atmospheric distillate as a by-product. In view of
- the fact that when the former method is applied to asphaltic
bitumen, yields are low, only the latter method is el.igible for
.~
7~
-- 2 --
the preparation of heavy product with a low RCT from asphaltic
bitumen or from mixtures of asphaltic bitumen and distillation
residue. A drawback to the latter method, however, is that it
gives rise to the formation of an undesirable C4 fraction
which, moreover, contributes considerably to the hydrogen
consumption of the process.
It was found that during the reduction of the RCT through
catalytic hydrotreatment of heavy hydrocarbon mixtures,
according as the catalytic hydrotreatment is carried out under
] more severe conditions in order to attain a greater RCT
reduction, the parameter "C4 production per % RCT reduction"
(for the sake of brevity hereinafter referred to as "G") at
first remains virtually constant (G ) and subsequently shows a
fairly sharp increase. In view of the hydrogen consumption of
the process it is however important to take care that the RCT
reduction is not carried beyond the value corresponding to
G = 2 x G . This means that in practice there will be a number
of cases in which it is undesirable, starting from a heavy
hydrocarbon mixture, to employ nothing but a catalytic hydro~
treatment for preparing a product from which , after separation
of an atmospheric distillate, an oil can be obtained which has
an initial boiling point of TlC and an RCT of a %w. In those
cases there is nevertheless an attractive manner of preparing an
oil having the afore-mentioned initial boiling point and RCT
from a heavy hydrocarbon mixture. To this end the product
obtained in the catalytic hydrotreatment is separated by
distillation into an atmospheric distillate and an atmospheric
residue having an initial boiling point of TlC. The process may
be continued in two ways. Flrst, from the atmosperic residue so
much asphaltic bitumen may be separated by solvent deasphalting
that a deasphalted atmospheric residue is obtained which has the
desired RCT of a %w. Secondly, the atmospheric residue may be
separated by distillation into a vacuum distillate and a vacuum
residue, and from the vacuum residue so much asphaltic bitumen
may be separated by solvent deasphalting that a deasphalted
vacuum residue is obtained having an RCT which is such that,
when this deasphalted vacuum residue is mixed wit~l the
previously separated vacuum disti]late, an oil is obtained which
has the desired RCT of a %w. The most attractive ~alance between
yields of C4 fractlon, C5 atmospheric distillate, asphaltic
bitumen and oil having an initial boiling point of TlDC and an
RCT of a %w is obtained when the catalytic hydrotreatment is
carried out under such conditions that G lies between 1.5 x G
and 2.0 x G . When the catalytic hydrotreatment is carried out
under such conditions that G < 1.5 x G , a low C4 production is
still obtained, but the yield of oil having an initial boiling
point of TlDC and an RCT of a %w in the combination process is
unsatisfactory. When the catalytic hydrotreatment is carried out
under such conditions that G > 2.0 x G , a high yield oE oil
;5 having an initial boiling point of TlC and an RCT of a %w is
still obtained in the combination process, but it is attended
with an unacceptably high C4 production.
G as well as the conditions at which G reaches a value
between 1.5 x G and 2.0 x G may be read from a graph composed
on the basis of a number of catalytic hydrotreatment scouting
experiments with the asphaltenes-containing hydrocarbon mixture
carried out at different severities and in which the occurring
G's have been plotted against the severities applied. Apart from
one parameter e.g. the space velocity, which is variable, the
other conditions in the scouting experiments are kept constant
and chosen equal to those which will be used when the process is
applied in practice.
The present patent application therefore relates to a
process for the preparation of a hydrocarbon mixture with an RCT
of a %w and an initial boiling point of TlDC, in which an
asphaltenes-containing hydrocarbon mixture is subjected to a
catalytic hydrotreatment J the product obtained being separated
by distillation into an atmospheric distillate and an
- atmospheric residue having an initial boiling point of TlC, in which either a deasphalted atmospheric residue having the
77~
-- 4 --
desired RCT of a %w is obtained from the said atmospheric
residue by solvent deasphalting, or in which the atmospheric
residue is first separated by distillation into a vacuum
distilla~e and a vacuum residue, from which vacuum residue
asphaltic bitumen is separated by solvent deasphalting such that
a deasphalted vacuum residue is obtained having an RCT such
that, when this latter deasphalted vacuum residue is mixed with
the said vacuum distillate, a mixture having the desired RCT of
a C/~w is obtained, the catalytic hydrotreatment being carried out
under such conditions that the C4 production per % RCT
reduction (G) lies between 1.5 x G and 2.0 x G . G represents
the virtually constant value of G which appears when the
catalytic hydrotreatment is carried out at low severity.
As regards the way in which RCT's of hydrocarbon mixtures
are determined, the following three cases may be distinguished.
a) The viscosity of the hydrocarbon mixture to be investigated
is so high that it is impossible to determine the RCT by
ASTM method D 524. In this case, the CCT (Conradson Carbon
Test value) of the mixture is determined by ASTM method
D 189, and the RCT is computed from the CCT according to
the formula:
RCT = 0.649 x (CCT)
b) The viscosity of the hydrocarbon mixture to be investigated
is such that the RCT can still be determined according to
the ASTM D 524 method, but this method gives an RCT value
which lies above 20.0 %w. In this case, as in the case
mentioned under a), the CCT of the mixture is determined by
ASTM method D 189 and the RCT is computed from the CCT
according to the formula mentioned under a).
c) The viscosity of the hydrocarbon mixture to be investigated
is such that the RCT can be determined by ASTM method D 524
and this method gives an RCT value not higher than 20.0 %w.
In this case the value thus found is taken to be the RCT of
- the mixture concerned.
77~
In practice, for the determination of the RCT's of vacuum
distillates, atmospheric residues, deasphalted distillation
residues and mixtures of vacuum distillates and deasphalted
distillation residues, the direct method described under c) will
in many cases be sufficient. In the determination of the RCT of
vacuum residues both the direct method described under c) and
the indirect method described under b) are used. In the
determination of the RCT of asphaltic bitumen the indirect
method described under a) is usually the only one eligible.
The process according to the invention is a two-step
process in which reduction of the RCT is attained through
reduction of the asphaltenes content. In the first step of the
process the asphaltenes content is reduced by converting part of
the asphaltenes by means of a catalytic hydrotreatment. In the
second step OI the process the asphaltenes content is reduced
by separating part of the asphaltenes by means of solvent
deasphalting. Asphaltenes containing hydrocarbon mixtures
usually contain an appreciable percentage of metals, especially
vanadium and nickel. When such mixtures are subjected to a
catalytic treatment 9 e.g. a catalytic hydrotreatment for RCT
reduction, as in the process according to the invention, these
metals will be deposited on the RCT-reduction catalyst, thus
shortening its life. In view of this, asphaltenes-containing
hydrocarbon mixtures having a vanadium + nickel content of more
than 50 ppmw should preferably be subjected to de~etallization
before being contacted with the RCT-reduction catalyst. This
demetallization may very suicably be carried out by contacting
the mixture in the presence of hydrogen, with a catalyst
consisting of more than 80 %w of silica. Both catalysts
consisting entirely of silica and catalysts containing one or
more metals having hydrogenating activity, in particular a
combination of nickel and vanadium, on a carrier substantially
consisting of silica, are eligible for the purpose. ~ery
suitable demetallization catalysts are those which meet certain
given requirements as regards their porosity and particle size
7~D
and which are described in Canadian patent Mo. 1,005,777. When in
the process according to the invention a catalytic demetallization
in the presence of hydrogen is applied to the hydrocarbon mi~-ture,
this demetallization may be carried out in a separate reactor.
Since the catalytic demetallization and the catalytic RCT reduction
can be carried out under the same conditions, both processes may
very suitably be carried out in the same reactor containing,
successively, a bed of demetallization catalyst and a bed of RCT-
reduction catalyst.
It should be noted that in the catalytic demetallization
the reduction of the metal content is accompanied by some reduction
of the RCT. The same applies to the catalytic RCT reduction in
which the RCT reduction is accompanied by some reduction of the
metal content. In this patent application, RCT reduction should be
taken to be the total RCT reduction occurring in the catalytic
hydrotreatment (i.e. including the RCT reduction occurring in a
possible catalytic demetallization process).
Suitable catalysts for carrying out the catalytic RCT
reduction are those which contain at least one metal chosen from
the group formed by nickel and cobalt and, in addition, at least
one metal chosen from the group formed by molybdenum and tungsten
on a carrier, which carrier consists more than 40 %w of alumina.
~ery suitable RCT~reduction catalysts are those which comprise the
metal combination nickel/molybdenum or cobalt/molybdenum on alumina
as the carrier.
The catalytic RCT reduction is preferably carried ou-t at
a temperature of 300-500C, a pressure of 50-300 bar, a space
-1 -1
velocity o~ 0.02-10 g.g .h and a H2/feed ratio of 100-5000 Nl/kg.
_ ~; _
., ~
Particular preference is given to carrying out the
catalytic RCT reduction at a temperature of 350-450C, a pressure
of 75-200 bar, a space velocity o:E 0.1.2 g.g l.h 1 and a H2/feed
ratio of 500-2000 Nl/kg. As regards the conditions to be used in
a ca.taly-tic demetallization process in the presence of hydrogen,
to be carried out if necessary, the same preference
-~a-
. j ,
'7~
applies as that stated hereinbefore for the catalytic RCT
reduction.
The desired RCT reduction in ~he first step of the process
according to the invention may, for instance, be achieved by
¦ 5 application of the space velocity pertaining to that RCT
reduction, which can be read from a graph composed on the basis
of a number of catalytic hydrotreatment scouting experiments
with the asphaltenes-containing hydrocarbon mixture carried out
at different space velocities and in which the RCT reductions
]0 achieved have been plotted against the space velocities used.
Apart from the space velocity, which is variable, the other
conditions in the scouting experiments are kept constant and
chosen equal to those which will be used when the process
according to the invention is applied in practice.
]5 The second step of the process according to the invention
is a solvent deasphalting step applied to a residue from the
distillation of the hydrotreated product of the first step. The
distillation residue to which the solvent deasphalting step is
applled may be an atmospheric residue or a vacuu~ residue from
the hydrotreated product. Preferably, a vacuum residue from the
hydrotreated product is used for the purpose. Suitable solvents
¦ for carrying out the solvent deasphalting are paraffinic hydro-
carbons having 3-6 carbon atoms per molecule, such as n-butane
and mixtures thereof, such as mixtures of propane with n-butane
and mixtures of n-butane with n-pentane. Suitable solvent/oil
weight ratios lie between 7:1 and 1:1 and in particular between
4:1 and 2:1. The solvent deasphalting is preferably carried out
at a pressure between 20 and lO0 bar. When n-butane is used as
the solvent, the deasphalting is preferably carried out at a
pressure of 35-45 bar and a temperature of 100-150C.
When the RCT reduction in the second step of the process
.according to the invention takes place by solvent deasphalting
of an atmospheric residue, the desired RCT of the deasphalted
atmospheric residue may be attained, for instance, by using the
deasphaltlng temperatore pertaining to that RCT, which can be
77~
-- 8 --
read from a graph composed on the basis of a number of de-
asphalting scouting experiments with the atmospheric residue
carried out at different temperatures in which the RCT's of the
deasphalted atmospheric residues obtained have been plotted
against the temperatures applied. Apart from the temperature,
which is variable, the other conditions in the scouting
experiments are kept constant and chosen equal to those which
will be used when the process according to the invention is
applied in practice.
]0 When the RCT reduction in the second step of the process
according to the invention takes place by solvent deasphalting
of a vacuum residue, afeer which the deasphalted vacuum residue
is mixed with the vacuum distillate separated earlier, the RCT
and the quantity of the deasphalted vacuum residue should be
]S adjusted to the quantity and the RC~T of the vacuum distillate as
follows. When a given quantity of vacuum distillate (VD) of A
pbw having a given RCTVD is available, then, in order to obtain
a mixture M having a given RCTM by mixing the vacuum distillate
with deasphalted vacuum residue (DVR), B pbw of deasphalted
vacuum residue will have to be prepared, its RCTDVR being such
that it obeys the relation:
A x RCTvD + B x RCTDVR
or, expressed otherwise,
A(RCTM - RCTVD) = B(RCTDVR - RCTM).
In the equation mentioned hereinabove the left-hand member
is known. In addition, in the right-hand member RCTM is known.
On the basis of a number of deasphalting scouting experiments
carried out with the vacuum residue at, for instance, different
- temperatures, a graph can be composed in which the term B(RCTD~TR
- RCTM) has been plotted a~ainst the temperature used. The
7~
g
temperature to be applied in the deasphalting in the second step
of the process according to the invention may be read from this
graph, this being the temperature at which the term
B(RCTDVR ~ RCTM) has the given value A(RCTM - RCTVD). Apart from
the temperature, which i5 variable7 the other condi~ions in the
scouting experiments on deasphalting are kept constant and
chosen equal to those which will be applied when the process
according to the invention is used in practice.
Besides the RCT, the metal content is also an important
parameter in assessing the suitability of heavy hydrocarbon oils
as feeds for catalytic conversion processes, in the presence or
absence of hydrogen, for the preparation of light hydrocarbon
distillates, such as gasoline and kerosine. According as the
feed has a higher metal content, the catalyst will be de-
activated more rapidly in these processes. As a rule, residualfeed mixtures have not only too high an RCT, but also too high a
metal content to be suitable, without treatment, as feeds for
the afore-mentioned catalytic conversion processes. The product
obtained in the process according to the invention is a de-
asphalted atmospheric residue or a mixture of a vacuumdistillate and a deasphalted vacuum residue, which product, in
addition to a low RCT, has a very low metal content. This is due
to a conslderable extent to the fact that the metal-containing
distillation residue which is subjected to solvent deasphalting
has been catalytically hydrotreated. For, the solvent de-
asphalting of such metal-containing residues shows a very high
metal-removing selectivity.
As examples of asphaltenes-containing hydrocarbon mixtures
which may be used as feed for the process according to the
invention the following may be mentioned:
a) atmospheric residues obtained in the distillation of a
crude mineral oil,
b) vacuum residues obtained in the distillation of a crude
mineral oil,
7~
-- 10 --
c) asphaltic bitumen separated in the solvent deasphalting of
the residues mentioned under a) and b) 3
d) asphaltlc bitumen separated ln the solvent deasphalting of
residues obtained in the distillation of a hydrotreated
residual fraction of a crude mineral oil,
e) mixtures of two or more of the heavy hydrocarbon mixtures
mentioned under a) - d),
f) heavy crude oils,
g) heavy hydrocarbon mixtures extracted from tar sands,
10 h) residues ex thermal cracking, and
i) mixtures of one or more of the asphaltenes-rich hydrocarbon
mixtures mentioned under a) - h) with one or more
asphaltenes-poor or asphaltenes-free hydrocarbon mixtures
such as aromatic extracts ex lubricating oil production and
cycle oils and slurry oils ex catalytic cracking.
As asphaltenes-containing hydrocarbon mixtures to be used
as feed for the process according to the invention the following
six are preferred:
Feed 1
20 An atmospheric residue obtained in the distillation of a crude
mineral oil.
The investigation has shown that the RCT reductions in the
catalytic hydrotreatment in which for G values are reached which
correspond with 1.5 x Gc and 2.0 x Gc, are dependent on Tll the
25 RCT of the atmospheric residue (b %w) and the percentage by
weight of the atmospheric residue which boils bel.ow 520C
(d %w), and are given by the following relation (relation 1)
RCT reduction = - x 100 =
b
51.6 - G.526 x d - 0.115 x Tl + 2.55 x b + 0.00115 x Tl x d
(1.426 - 1.15 x 10 x Tl)(l - 0.01 x d)
where c is the RCT of the atmospheric residue with an initial
boiling point of TlC of the hydrotreated product.
7~3
-- 11 --
Feed 2
A vacuum residue obtained in the distillation of a crude mineral
oil.
The investigation has shown that the RCT reductions in the
catalytic hydrotreatment in which for G values are reached which
correspond with 1.5 x G and 2.0 ~ G , are depende~t on Tl, the
RCT of the vacuum residue (b %w) and the 5 %w boiling point of
the vacuum residue (T5C), and are given by the following
relation (relation 2)
RCT reduction = b c x 100 =
b
73.5 - 0.108 x Tl + 2.55 x b - 0.05 x T5
1.4 - 1.08 x lO 3 x Tl
where c is the RCT of the atmospheric residue with an initial
boiling point of TlC of the hydrotreated product.
Feed 3
An asphaltic bitumen separated in the solvent deasphalting of a
distillation residue from a crude mineral oil.
The investigation has shown that the RCT reductions in the
catalytic hydrotreatment in which for G values are reached which
correspond with 1.5 x G and 2.0 x G , are dependent on Tl, the
RCT of the asphaltic bitumen (b %w) and the average molecular
weight (M) of the asphaltic bitumen, and are given by the
following relation (relation 3)
2~7Q
-- 1 2 --
V
o
o
E~
o
a
.
r~ rl
r-l .Q
O ~ rl
O ~D V
~ r~
Yl ~ I ~ ~
D ~ E-l
tl oo X
~' O ~ ~
rl _1- O
X ~r~
U~
t-l r-1 O t-l
E~ X ~
_I I
~i ~ rC
~ ~ p~
E~ ~d
. ~
0~
_ ~
O O
l E~
U~ ~ tO
~C~ t~
V
rl ~-d
~1)
:' U
h t'l
7~
- 13 -
Feed 4
A mixture of an atmospheric residue obtained in the distillation
of a crude mineral oil and an asphaltic bitumen separated in the
solvent deasphalting of a residue obtained in the distillation
S of a hydrotreated residual fraction of a crude mineral oil,
which mixture comprises less than 50 pbw of the asphaltic bitumen
per 100 pbw of the atmospheric resldue.
The investigation has shown that the RCT reductions in the
catalytic hydrotreatment in which for G values are reached which
] correspond to 1.5 x G and 2.0 x G , are dependent on
1) Tl,
2) the RCT of the atmospheric residue (b %w)~
3) the percentage by weight of the atmospheric residue boiling
below 520DC ~f %w),
IS 4) the RCT of the asphaltic bitumen (c %w), and
5) the asphaltic bitumen/atmospheric residue mixing ratio in
the feed mixture, expressed in pbw of the asphaltic bitumen
per 100 pbw of the atmospheric residue (r pbw),
and are given by the following relation (relation 4)
27~G~
+ o C~
o _,
X
Lr .,,
+,
,,
g ~ X ,~
o
X ~ o ra
I o
~ ,~
,,, ~_
_~ r~
~_
,,4 X
. , ~ ~
V
_. o ` 3
+ X
E~~ 5
P~X In ~ r~
U~ _~ ~
U~ ~ ~ ~
h CJ U
E~
x a) o
4~ X ~rl rl h
X
O
.
O 4
l U~ X
r-l _I ~0 V Ll O
~ .
_~ ~ X + O O ~
X I oO ~ , 5
~) ~ ~
X ~ ~ ~C
_~ ~ O
O ~ 11 11 11
o
3~
Feed 5
A mixture of a vacuum residue obtained in the distillation of a
crude mineral oil and an asphaltic bitumen separated in the
solvent deasphalting of a residue obtained in the distillation
¦ 5 of a hydrotreated residual. fraction of a crude mineral oil 3
which mixture comprises less than 50 pbw of the asphaltic bitumen
per 100 pbw of the vacuum residue.
The investigation has shown that the RCT reductions in the
catalytic hydrotreatment in which for G values are reached which
correspond to 1.5 x G and 2.0 x G , are dependent on
1) Tl ~
2) the RCT of the vacuum residue (b %w),
3) the 5 ~DW boiling point of the vacuum residue (15C),
4) the RCT of the asphaltic bitumen (c %w)g and
]5 5) the asphaltic bitumenivacullm residue mixing ratio in the
feed mixture, expressed in pbw of the asphaltic bitumen per
100 pbw of the vacuum residue (r pbw),
and are given by the relatioD (relation 5)
7~7~
h E~
O O O
' O ~1
X O
U~
Il e
o +l
O ~ ~1
o
X
Il co e
o _~
rl +
0 r~
-- 3
X X
~; O
.
O ~
+ O ~
~ ).1 U U
2 E~
~ h
X X X .C
u~ ' e U~
. O ~:1 0 ~
l X
U
U~ C~ ~ ~ ~
. O X rC .e .-
~o . ~ ~ ~ o
X ~ o ~
_, ~ X.
~4 o U
o ~ e 4
~ JJ O
o a) I ll ll
--I 3 P~ ~O o.)
~ 277~
- 17 -
Feed 6
A mixture of an asphaltic bitumen I separated in the solvent
deasphalting of a residue obtained in the disti~lation of a
crude mineral oil and an asphaltic bitumen II separated in the
solvent deasphalting of a residue obtained in the distillation
of a hydrotreated resi.dual fraction of a crude mineral oil which
mixture comprises less than 50 pbw of asphaltic bitumen II per
100 pbw of asphaltic bitumen I.
The investigation has sho~m that the RCT reductions in the
]0 catalytic hydrotreatment in which for G values are reached which
correspond to 1.5 x G and 2.0 x G , are dependent on
1) Tl,
2) the RCT of the asphaltic bitumen I (b %w),
3) the average molecular weight of the asphaltic bitumen I
(M),
4) the RCT of the asphaltic bitumen II (c %w), and
5) the asphaltic bitumen II/asphaltic bitumen I mixing ratio
in the feed mixture, expressed in pbw of the asphaltic
bitumen II per lO0 pbw of the asphaltic bitumen I (r pbw) 3
and are given by the relation (relation 6)
-- 18 ~
g
X
+,
P~ ~
._
~ E~
_ o
+
~ t-~
~~ ,o
O ~ ~ O
D ~ ~1
K t~ ~,~
~ ~ ~ ,~
,1 ~ _
~D + J~
a~ oo _~ 3
_I E~
E~ X
~)
o~
~0
O Q~ ~
X O K O o
_~
.
C`l I ~ ~ ~
l ~
_l C~
ao .D X ~c: S
K X ,c:~ ~ ol
_~ O
--~ ~ o
O ~J 11 11 11
o
7D7~
-- 19 --
The average molecular weight M of the asphaltic bitumen I
used as feed component in feed 6 as well as the average
molecular weight M of the asphaltic bitumen used as feed 3 are
determined by ASTM method D 3592-77 using toluene as solvent.
The relations 1-6 mentioned above offer an opportunity of
determining whether, in view of the maximum acceptable value of
G (corresponding to 2.0 x G ), it is possible by catalytic
hydrotreatment alone, starting from the feeds 1-6, to prepare a
product from which, by distillation, an atmospheric residue can
be obtained which has a given initial boiling point of TlC and
a given RCT of a %w. If, according to the relations, this proves
impossible and, therefore, the combination route has to be
applied, the relations further indicate the limits between
which, in the catalytic hydrotreatment of the combination route,
the RCT reductions should be chosen to ensure optimum efficiency
of the combination route.
The feeds 4-6 are composed of two blending components. One
of these blending components (blending component I) is selected
from the group consisting of atmospheric residues obtained in
the distillation of a crude mineral oil, vacuum residues
obtained in the distillation of a crude mineral oil and asphaltic
bitumen separated in the solvent deasphalting of a residue
obtained in the distillation of a crude mineral oil. The other
blending component (blending component II) is an asphaltic
bitumen separated in the solvent deasphalting of a resLdue
obtained in the distillation of a hydrotreated residual fraction
of a crude mineral oil. Examples of the latter residual
fractions are atmospheric residues and vacuum residues obtained
in the distillation of a crude mineral oil and asphaltic bitumen
separated in the solvent deasphalting of these residues. A very
attractive embodiment of the proçess according to the invention
in which one of the feeds 4-6 is used, is that in which the
blending component II used 8S a component of the feed for the
first step is the asphaltic bitumen obtained in the solvent
- 20 -
deasphalting in the second step. The conditions for attaining
the desired RCT reduction in the first step of the process, with
recirculation of asphaltic bitumen, may be determined as
follows. The relation found is used to determine the RCT
reduction to be employed in the catalytic hydrotreatment in
order to ensure optimum efficiency in the combination process,
when blending component I is the only feed used. The space
velocity to be used for the purpose is detennined on the basis
of a number of catalytic hydrotreatment experiments using
]0 blending component I as the feed. ~sing this space velocity, in
the combination process, an oil is prepared which has the
desired RCT of a %w and the desired initial boiling point of
TlC, and an asphaltic bitumen (asphaltic bitumen A) is obtained
as a by-product. Subsequently, the relation found is used to
determine the RCT reduction to be employed in the catalytic
hydrotreatment in order to ensure optimum efficiency in the
combination process when a mixture of blending component I and
asphaltic bitumen A having the desired ratio r is used as the
feed. The space velocity to be used for the purpose is
determined on the basis of a number of catalytic hydrotreatment
scouting experiments using the mixture of blending component I
and asphaltic bitumen A as the feed. Using this space velocity
in the combination process an oil is prepared which has the
desired RCT of a %w and the desired initial boiling point of
TlC, and an asphaltic bitumen (asphaltic bitumen B) is obtained
as a by-product. These experiments are repeated optionally once
or several times, in each case using the asphaltic bitumen
separated from a preceding series of experiments as the mixing
component for blending component I (at constant values of r) in
a following series of experiments~ until the moment has come
when two successive series of experiments yield separated
asphaltic bitumens having virtually equal RCT's. Thus the space
velocity is determined wnich is required for the application in
actual practice of the process according to the invention with
recirculation of asphaltic bitumen. Generally, two or three
7q3
- 21 -
series of experiments are sufficient to produce the stationary
state.
The invention is now illustrated with the aid of the
following examples.
EXAMPLE 1
, _ ,
In the investigation two atmospheric residues were used
which had been obtained in the distillation of crude mineral
oils (Atmospheric residues A and B).
Atmospheric residue A had an RCT of 10 %w (determined by
ASTM method D 524), a vanadium + nickel conten~ of 70 ppmw and a
percentage boiling below 520C of 50 %w.
Atmospheric residue B had an RCT of 15.6 %w (determined by
ASTM method D 524), a vanadium + nickel content of 500 ppmw and
a percenta~e boiling below 520C of 29.4 %w.
As regards the question whether it is possible, in view of
the maximum permissible value of G, starting from atmospheric
residue A, to prepare by nothing but catalytic hydrotreatment a
product from which, by distillation, an atmospheric residue can
be obtained which has an initial boiling point of 370C and an
RCT lower than that of atmospheric residue A, application of
relation 1 in the form
- x 100 = F
b max
(where F is the maximum value of the right-hand member of the
max
relation), with substitution of b=10~ T=370 and d=50, shows that
this is quite feasible provided that the atmospheric residue
with an initial boiling point of 370C to be prepared has an RCT
(c) higher than 3.6 %w. This means, for instance, that, starting
from atmospheric residue A, for the preparation of an
atmospheric residue having an initial boiling point of 370C and
an RCT (c) of 4.5 %w a catalytic hydrotreatment alone will be
sufficient.
If, however, from atmospheric residue A an oil is to be
prepared having an initial boiling point of 370C and a much
'77(~
- 22 -
more reduced RCT of 1.5 %w a catalytic hydrotreatment alone is
not sufficient in view of the maximum permissible value of G.
Then, in addition to the catalytic hydrotreatment, a solvent
deasphalting treatment should be applied. Application of
relation 1, in the form:
maximum RCT reduction = F , and
max
minimum RCT reduction = F
min
(where F and F . are the maximum and the minimum value,
max mln
respectively, of the right-hand member of the relation), with
substitution of b-10, T=370 and d=50, shows that for optimum
utilization of the combination process care should be taken that
the RCT reduction in the catalytic hydrotreatment is between
54.1 and 64.1%.
With the obJect of preparing atmospheric residues having an
initial boiling point of 370C and different RCT's (c),
atmospheric residue A was subjected to catalytic hydrotreatment
in thirteen experiments. The experiments were carried out ln a
1000 ml reactor containing two fixed catalyst beds of a total
volume of 600 ml. The first catalyst bed consisted of a
Ni/V/SiO2 catalyst containing 0.5 pbw of nickel and 2.0 pbw of
vanadium per 100 pbw of silica. The second catalyst bed consisted
of a Co/Mo/A1203 catalyst containing 4 pbw of cobalt and 12 pbw
of molybdenum per 100 pbw of alumina. The weight ratio between
the Ni/V/SiO2 and Co/Mo/A1203 catalysts was 1:3. All ~he experi-
ments were carried out at a temperature of 390C, a pressure of125 bar and a H2/oil ratio of 1000 Nl/kg. Various space
velocities were used in the experiments. The results of Experi-
ments 1-13 at run hour 450 are listed in Table A.
For each experiment the table gives the space velocity
30 used, the RCT reduction (b~c x 100) achieved and the corre-
bsponding C4 production (calculated as ~w on feed).
Experiments 1-12 were carried out in pairs, the difference
in space velocity between the two experiments of each pair
being such as to achieve a difference in RCT reduction
77~
- 23 -
of about 1.0%. The table further gives the C~ production per
RCT reduction (G) for each pair of experiments.
TABLE A
~ .
Experiment Space RCT C4 G,
No. velocity, reduction, production,
~ % %w on feed~/~w
1 1.50 31.9 0.481 1
~0.015
2 1.40 32.9 0.496 J
3 2.42 20.0 0.300
0.015
4 2.31 21.3 0.319
1.07 40.2 0.603 1
0.016
~ 1.03 41.1 0.617 )
7 0.61 53.5 0.901
0.023
8 0.57 54.7 0.929
9 0.40 63.4 1.164 ~
0.030
0.37 64.6 1.200
11 0.30 70.0 1.432 ~
~ 0.057
12 0.27 71.1 1.495 J
13 0.50 59.0 1.030
77~
- 2~ -
Only Fxperiments 8, 9 and 13 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. ~5 can be seen in Table A, in Experiments
1-2, 3-4 and 5-6, G remains virtually constant (G ). In Experi
ments 7-8 and 9~10, in which RCT reductions were achieved of
about 54 and 64~, respectively, G was about 1.5 G and 2.0 G ,
respectively.
The products obtained in the catalytic hydrotreatment
carried out according to Experiments 5, 11 and 13 were separated
by successive atmospheric distillation and vacuum distillation
into a C4 fraction, a H2S + N~13 fraction, a C5-370C atmos
pheric distillate, a 370-520~C vacuum distillate and a 520C
vacuum residue. The vacuum residues were deasphalted with
n-butane at a pressure of 40 bar and a solvent/oil weight ratio
of 3:1~ and the deasphalted vacuum residues obtained were mixed
with the corresponding vacuum distillates. The results (of which
only Experiment 16 is an experiment according to the invention)
are listed in Table B.
77~
~ 25 -
TABLE B
Experiment No. 14 15 16
H2-treated product from
Experiment No. 5 11 13
Distillation
Yield of products calculated
on 100 pbw feed, pbw
C4 0.60 1.43 1.03H2S ~ NH3 2.9 3.4 3.2C5 - 370C 8.2 11.7 10.5
370-520C (vacuum distillate) 56.3 58.0 58.1
520C+ (vacuum residue) 33.3 27.7 28.9
RCT of the vacuum distillate, %w 0.4 0.3 0.3RCT of the vacuum residue, ~w 15.4 8.8 13.6
Deasphalting
Temperature, ~C 130 129 133Yield of deasphalted vacuum
residue, pbw 21.6 22.1 21.8Yield of asphaltlc bitumen, pbw 11.7 5.6 7.1RCT of the deasphalted vacuum
residue, %w 4.4 4.6 4.8
Mixing
Yield of mixture of vacuum
dlstillate and deasphalted
vacuum residue, pbw 77.9 80.1 79.9Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w 1.5 . 1.5 1.5
- 26 -
Applica~ion oE relation 1, in ~he form:
- x 100 = F
b max
with substitution of b=15.6, T=370 and d=29.4, shows that this
is quite feasible to prepare an atmospheric residue with an
initial boiling point of 370C and an RCT lower than that of
atmospheric residue B by catalytic hydrotreatment and distil-
lation of the product so obtained 9 provided that the atmospheric
residue to be prepared has an RCT (c) higher than 4.7 %w.
If from atmospheric residue B however an oil is to be
prepared which has an initial boiling point of 370C and a much
10 more reduced RCT of 2.5 70W9 a catalytic hydrotreatment alone is
insufficient in view of the maximum permissible value of G.
Then, in addition to the catalytic hydrotreatment a solvent
deasphalting step should be applied. Application of relation 1,
in the fonn:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F i
with substitution of b=15.6, T=370 and d=29.4, shows ~hat or
optimum utilization of the combination process care should be
taken that the reduction in the catalytic hydrotreatment is
20 between 60.0 and 70.0%.
With the object of preparing an oil having an initial
boiling point of 370C and an RCT of 2.5 70W from atmospheric
residue B this atmospheric residue B was sub~ected to a catalytic
hydrotreatment in a similar way as described for Experiments
1-13, using the same catalysts. The reaction conditions were
slightly different, viz. a temperature of 395C, a pressure of
150 bar, a space velocity of 1.05 g.g .h and a H2/oil ratio
of 1000 Nl/kg. The RCT reduction was 65%. The product of the
catalytic hydrotreatment was separated likewise as described
30 hereinbefore by consecutive atmospheric distillation and vacuum
distillation into several fractions. The 520C vacuum residue
was deasphalted with n-butane at a temperature of 115C, a
pressure of ~0 bar and a solvent/oil weight ratio of 3:19 and
- 27 -
the deasphalted vacuum residue obtained was mixed with the
vacuum distillate. The results of this experiment No. 17
according to the invention are given hereinafter.
Experiment No. 17
Distillation
Yield of products calculated on 100 pbw feed, pbw
C4 0.9
1~2S + NH3 1.5
C5 - 370C 14.2
370-520C (vacuum distillate) 48.3
520C (vacuum residue) 32.6
RCT of the vacuum distillate, %w 0~5
RCT of the vacuum residue, %w 12.9
Deasphalting
Yield of deasphalted vacuum
residue, pbw 26.8
Yield of asphaltic bitumen, pbw 5.8
RCT of the deasphalted vacuum
residue, %w 6.1
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 75.1
Initial boiling point of the
mixture, C 370
RCT of the mixture, ~/~w 2.5
EXAMPLE 2
In the example two different vacuum residues were used:
(i) Vacuum residue A with an RCT of 19 %w (determined by ASTM
77~3
- 28 -
method D 524), a vanadium -~ nickel content of 160 ppmw and
a 5 %w boiling point of 500C, and
(ii) Vacuum residue B with an RCT of 11 %w (determined by ASTM
method D 524), a vanadlum ~ nickel content of 20 ppmw and a
5 %w boiling point of 520C.
From vacuum residue A an oil having an initial boiling
point of 370C and an RCT of 2.5 %w cannot be prepared by
catalytic hydrotreatment alone in view of the maximum
permissible value of ~. Then, in addition to the catalytic
10 hydrotreatment, a solvent deasphalting treatment should be
applied.
Application of relation 2 in the form:
maximum RCT reduction = FmaX, and
minimum RCT reduction = F
min
15 (where Fmax and Fmin are the maximum and the minimum value,
respectively, of the right-hand member of the relation), with
substitution of b=l9, Tl-370 and T5=500, shows that for optimum
utilization of the combination process care should be taken that
the RCT reduction in the catalytic hydrotreatment is between
20 52.0 and 62.0%.
With the object of preparing atmospheric residues having an
initial boiling point of 370C and different RCT's (c), vacuum
residue A was subjected to catalytic hydrotreatment in thirteen
experiments in a similar way as described for Experiments 1-13,
25 using the same catalysts in the weight ratio indicated. The
reaction conditions were: a temperature of 385C~ a pressure of
150 bar and a H2/oil ratio of 1000 Nl/kg. Various space
velocities were used in the experiments. The results of
Experiments 18-30 at run hour 500 are listed in Table C.
~ ~ ~2~7~
- 29 -
TABLE C
E~periment Space RCT C4 G,
No. velocity, r~ductlon, production,
~ .h ~/O %w on Eeed %w
18 0.91 30.5 0.801 `~
~ 0.027
19 0.87 31.5 0.828 J
1.36 20.0 0.525 1
0.027
21 1.30 21.2 0.557
22 0.60 39.9 1.061 1
~ 0.028
23 0.58 ~1.1 1.095 J
24 0.38 51.5 1.466 ~
0.040
~.36 52.4 1.502
26 0.26 61.8 1.983 ~
0.054
27 0.24 62.5 2.021
28 0.17 70.0 3.015 ~
0.113
29 0.15 71.1 3.139
0.30 57.0 1.700
77~
- 30 -
Only Experiments 25, 26 and 30 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. As can be seen in Table C in Experiments
18-19, 20-21 and 22-23, G remains virtually constant (Gc). In
5 Experiments 24-25 and 26-27, in which RCT reductions were
achieved of about 52 and 62%, respectively, G was about 1.5 G
and 2.0 G , re3pectively.
The products obtained in the catalytic hydrotreatment
carried out according to Experiments 22, 28 and 30 were
10 separated by consecutive atmospheric distillation and vacuum
distillation into several fractions as described hereinbefore.
The vacuum residues were deasphalted with n-butane and the
deasphalted vacuum residues so obtained were mixed with the
corresponding vacuum distillates. I'he results of these
15 experiments of which only Experiment 33 is an experiment
according to the invention, are listed in Table D.
~Z77C~
- 31 -
TABLE D
Experiment No. 31 32 33
H2-treated product from
Experiment No. 22 28 30
Distillation
Yield of products calculated
on 100 pbw feed, pbw
c4- 1.06 3.02 1.70
H2S + NH3 3.8 5.]. 4.5
C5 - 370C 5.8 10.0 8.3
370-520C (vacuum distillate) 23.5 39.0 34.0
520C (vacuum residue) 67.1 45.2 53.0
RCT of the vacuum distillate, %w 0.4 0.4 0.4
RCT of the vacuum residue, %w15.2 10.3 13.2
Deasphalting
Temperature, C 137 125 133
Yield of deasphalted vacuum
residue, pbw 41.0 36.2 38.0
Yield of asphaltic bitumen, pbw. 26.1 9.0 15.0
RCT of the deasphalted vacuum
residue, %w 3.7 4.8 4.4
Mixing
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 64.5 75.2 72.0
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, ~/~w 2.5 2.5 2.5
~&~7~
A ca~alytic hydrotreatment alone is insufEicient to
prepare from vacuum residue B an oil with an initial boiling
point of 370C and an RCT of 3 ~OW in view of the maximum
permissible value of G. In addi~ion to the catalytic hydro-
5 treatment a solvent deasphalting step has to be applied.
Application of relation 2, in the form:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F
min
shows that for optimum utiliæation of the combination process
10 care should be taken that the reduction in the catalytic hydro-
treatment is between 30.6 and 40.6%.
Vacuum residue B was subjected to a catalytic hydro-
treatment to prepare an oil having an initial boiling point of
370C and an RCT of 3.0 ~w from it. The experiment ~o. 34 was
15 carried out in a 1000 ml reactor containing a fixed catalyst bed
oE 600 ml volume of the same Co/Mo/Al203 catalyst as used in
Example 1. Reaction conditions were: a temperature of 390C, a
pressure of 125 bar, a space velocity of 1.0 g.g .h and a
H2/oil ratio of 1000 ~l/kg. The RCT reduction was 35.5%. The
20 520C vacuum residue obtained after vacuum distillation of the
product of the catalytic hydrotreatment was deasphalted with
n-butane at a temperature of 127C, a pressure of 40 bar and a
solvent/oil weight ratio of 3:1, and the deasphalted vacuum
residue obtained was mixed with the 370-520C vacuum
25 distillate. The results of this experiment according to the
invention are given hereinafter.
- 33 -
Experiment No. 34
Distillation
Yield of products calculated
on 100 pbw feed, pbw
4 1.4
H2S + NH3 1.0
C5 - 370C 3.5
370-520C (vacuum distillate) 20.6
520C (vacuum residue) 71.2
RCT of the vacuum distillate, %w 0.3
RCT of the vacuum residue, ~OW 9.1
Deasphalting
Yield of deasphalted vacuum
residue, pbw 56.0
Yield of asphaltic bitumen, pbw 15.2
RCT of the deasphalted vacuum
residue, %w 4.0
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 76.6
Initial boiling point of the
mixture, C 370
RCT of the mixture, %w 3.0
EXA~IPLE 3
In the following experiments two asphaltic bitumens were
used.
Asphaltic bitumen A had been obtained through deasphalting
with propane of a vacuum residue from a crude mineral oil. It
had an RCT of 25.4 %w (computed from the CCT determined by AS'rM
method D 189), an average molecular weight of 1400 (determined
7~
by ASTM method D 3592/77, using toluene as the solvent) and a
vanadium + nickel content o~ 250 ppmw.
Asphaltic bitumen B had been obtained by deasphalting with
n-butane of a vacuum residue from a crude mineral oil. It had an
RCT of 4~.0 %w (computed from the CCT determined by ASTM method
D 189), an average molecular weight of 2000 (determined by ASTM
method D 8592/77, using toluene as the solvent) and a vanadium +
nickel content of 420 ppmw.
Catalytic hydrotreatment alone is not sufficient to prepare
from asphaltic bitumen A an oil having an initial boiling point
of 370C and an RCT of 3.0 ~OW in view of the maximum permissible
value of G. Then, in addition to the catalytic hydrotreatment, a
solvent deasphalting treatment should be applied. Application of
relation 3, in the form:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F .
mln
shows that for optimum utilization of the combination process
care should be taken that the RCT reduction in the catalytic
hydrotreatment is between 51.0 and 61.4%.
Asphaltic bitumen A was subjected to catalytic hydro-
treatment in thirteen experiments to prepare atmospheric
residues having an initial boiling point of 370C and different
RCT's (c). The experiments were similar to those described for
Experiments 1-13, the weight ratio between the Ni/V/SiO2 and
25 Co/Mo/A1203 catalysts however being 1:2. The reaction conditions
were: a temperature of 400C, a pressure of 145 bar and a H2/oil
ratio of 1000 Nl/kg, and varying space velocities. The results
of Experiments 35-46 at run hour 450 are listed in Table E.
7~
- 35 -
TABLE E
Experiment Space XCT C4 G,
No.velocity,reduction, production,
g g-l h-l % %w on feed %w
35 0.61 30.2 1.054
0.030
36 0.58 31.3 1.087
37 0.91 19.8 0.689 1
0.030
38 0.88 20.7 0.716
39 0.40 39.8 1.390 1
0.032
0.38 41.0 1.428
41 0.27 50.8 1.880 )
0.044
42 0.25 51.7 1.920
43 0.18 60.6 2.528 ~
t 0.060
44 Q.17 61.8 2.600 J
0~11 70.5 3.996 1
0.~12
46 0.10 71.5 4.208
47 0.22 56.0 2.220
~&~7~
- 36 -
Only Experiments 42, 43 and 47 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. As can be seen in Table E in Experiments
35~36, 37-38 and 39-40, G remains virtually constant (G ). In
5 Experiments 41-42 and 43-44, in which RCT reductions were
achieved of about 51 and 61%, respectively, G was about 1.5 Gc
and 2.0 G , respectively.
The products obtained in the catalytic hydrotreatment
carried out according to Experiments 39, 45 and 47 were
10 separated by consecutive atmospheric distillation and vacuum
distillation into separate fractions. The 520C vacuum residues
were deasphalted with n-butane and the deasphalted vacuum
residues obtained were mixed with the corresponding 370-520C
vacuum distillates. The results are listed in Table F,
15 Experiment 50 being according to the invention.
77~
TABLE F
Experiment No. 48 49 50
H2-treated product from
Experiment No. 39 45 47
Distillation
Yield of products calculated
on 100 pbw feed, pbw
C4 1.39 4.00 2.22
2 NH3 3.0 4.0 3 4
C5 - 370C 13.9 19.4 17.0
370-520C (vacuum distillate) 13.2 22.0 13.4
520C (vacuum residue) 70.0 53.1 61.0
RCT of the vacuum distillate, %w 0.5 0.3 0.4
RCT of the vacuum residue, %w18.1 10.5 14.5
Deasphalting
Temperature, C 132 130 132
Yield of deasphalted vacuum
residue, pbw 39.8 41.9 41.5
Yield of asphaltic bitumen, pbw 30.2 11.2 18.5
RCT of the deasphalted vacuum
residue, ~/OW 3.8 4.4 4.2
Mixing
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 53.0 63.9 59.9
Initial boiling point of the
mixture, C 370 370 -370
RCT of the mixture, %w - 3.0 3.0 3.0
z~
- 38 -
A catalytic hydrotreatment alone is insufficient to
prepare from asphaltic bitumen B an oil having an initial
boiling point of 370C and an RCT of 4 %w in view of the maximum
permissible value of G. In addition to the catalytic
5 hydrotreatment a solvent deasphalting step should be applied.
Application of relation 3, in the form:
maximum RCT ~eduction = FmaX~ and
minimum RCT reduction = E .
mln
shows that for optimum utilization of the combination process
10 care should be taken that the reduction in the catalytic hydro~
treatment is between 56.1 and 66.5%.
Asphaltic bitumen B was subjected to a catalytic hydro~
treatment to prepare an oil having an initial boiling point of
370C and an RCT of 4.0 %w from it. The experiment was similar
15 to those described for Experiments 1-13, the weight ratio
between the Ni/V/SiO2 and Co/Mo/A12O3 catalysts however being
1:1. Reaction conditions were: a temperature of 390C, a
pressure of 150 bar, a space velocity of 0.41 g.g 1.h 1 and a
H2/oil ratio of 1000 Nl/kg. The RCT reduction was 61.0%. The
20 520C vacuum residue obtained after vacuum distillation of the
product of the catalytic hydrotreatment was deasphalted with
n-butane at a temperature of 120C, a pressure of 40 bar and a
solvent/oil weight ratio of 3:1, and the deasphalted vacuum
residue obtained was mi~ed with the 370-520C vacuum
25 distillate. The results of this experiment according to the
invention are given hereinafter.
- 39 -
Experiment No. 51
istillation
Yield of products calculated on 100 pbw feed, pbw
4 3.7
H2S ~ NH3 6.1
C5 - 370C 19.9
370-520C (vacuum distillate) 17.0
520C (vacuum residue) 55.6
RCT of the vacuum distillate, %w0.6
RCT of the vacuum residue, %w 24.2
Deasphalting
Yield of deasphalted vacuum
residue, pbw 33.9
Yield of asphaltic bitumen, pbw21.7
RCT of the deasphalted vacuum
residue, %w 5.7
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 50.9
Initial boiling point of the
mixture, ~C 370
RCT of the mixture, %w 4.0
EXAMPLE 4
In this experiment a mixture AB wa~s used which had been
obtained by mixing 100 pbw of an atmospheric residue A and 15
pbw of an asphaltic bitumen B. Atmospheric residue A had an RCT
5 of 9.8 %w (determined by ASTM method D 524), and a vanadium ~ -
nickel content of 95 ppmw and boiled below 520C to an extent of
50 %w. Asphaltic bitumen B had an RCT of 35 %w (calculated from
~ '~o -
the CCT determined by ASTM method D 189) and a vanadium ~ nickel
content oE 110 ppmw. Asphaltic bitumen B was obtained by solvent
deasphalting with n-butane of a vacuum residue obtained in the
distillation of a hydrotreated mineral oil vacuum residue.
A catalytic hydrotreatment alone is not sufficient to
prepare from mixture AB an oil having an initial boiling point
of 370C and an ~CT of 1.5 %w in view of the maximum permissible
value of G. Then, in addition to the catalytic hydrotreatment, a
solvent deasphalting treatment should be applied. Application of0 r~la~ion 4, in the form:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F .
mm
with substitution of b=9.8, c=35, r=15, Tl=370 and f-50, shows
that for optimum utilization of the combination process care
15 should be taken that the RCT reduction in the catalytic hydro-
treatment is between 34.6 and 46.2%.
A mixture AB was subjected to catalytic hydrotreatment in
eleven experiments to prepare atmospheric residues having an
initial boiling point of 370~C and differen~ RCT's (e). The
20 experiments were similar to those described for Experiments
lB-30, the weight ratio between the ~i/V/SiO2 and Co/Mo/A1203
~atalysts however being 1:2.5. The reaction conditions were: a
temperature of 385C, a pressure of 150 bar and a E12/oil ratio
of 1000 Nl/kg, with varying space velocities. The results of
25 Experiments 52-62 at run hour 425 are listed in Table G.
7~
TABLE G
Experlment Space RCT C~ G,
No. ve]ocity,reduction, production,
~ ~ ~w on feed %w
O
52 5.31 10.1 0.217
0.021
53 4.84 11.0 0.236
54 2.09 22.3 0.475
0.022
2.02 23.1 0.493
56 1.19 34.2 0.838
0.032
57 1.13 35.4 0.876
58 0.68 46.1 1.2~0 1
~ 0.042
59 0,~5 47.0 1.318 J
0.41 60.3 2.057 1
0.086
61 0.40 61.8 2.168 J
62 0.86 40.5 1.030
* RCT reduction = d e x 100%
7~
- 42 -
Only Experiments 57, 58 and 62 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. As can be seen in Table G in Experiments
52-53 and 54-55, G remains virtually constant (G ). In Experi-
5 ments 56-57 and 58-59, in which RCT reductions were achieved of
about 35 and 47%, respectively, G was about 1.5 x G and
2.0 x G , respectively.
The products obtained in the catalytic hydrotreatment
carried out according to Experiments 54, 60 and 62 were
10 separated by consecutive atmospheric distillation and vacuum
distillation into separate fractions and the 520C vacuum
residues were deasphalted with n-butane under standard
conditions. The results (of which only Experiment 65 is an
experiment according to the invention) are listed in Table H.
'77~
- 43 -
TABLE H
Experiment No. 63 64 65
H2-treated product from
Experiment No. 54 60 62
Distillation
_ .
Yield of products calculated
on 100 pbw feed, pbw
C4 0.5 2.1 1.0
H2S ~ NH3 1.6 3.1 2.8
C5 - 370C 9.5 14.0 12.3
370-520C (vacuum distillate) 43.7 50.1 48.8
520C~ (vacuum residue) 45.2 32.0 36.1
RCT of the vacuum distillate, %w 0.4 0.3 0.3
RCT of the vacuum residue, %w19.7 12.9 17.9
Deasphaltin~
Temperature, C 135 132 133
Yield of deasphalted vacuum
residue, pbw 22.0 22.4 21.8
Yield of asphaltic bitumen, pbw 23.2 9.6 14.3
RCT of the deasphalted vacuum
residue, %w 3.7 4.2 4.2
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 65.7 72.5 70.6
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w 1.5 1.5 1.5
Three further experiments (Experiments 66-68) were carried
out to prepare an oil having an initial boiling point of 370C
and an RCT of 1.5 70w. In the experiments three different
residual feedstocks were subjected to a c~talytic hydrotreatment
in the same reactor as described for Experiments 1-13 and
applying the same reaction conditions and catalysts at the
5 weight ratio indicated there. The products from the catalytic
hydrotreatment were further treated as described for Experiments
14, 15 and 16.
Experiment 66
The feed used in this experiment was atmospheric residue C.
10 Atmospheric residue C obtained in the distillation of a crude
mineral oil, had an RCT of 10 ~OW (determined by ASTM method D
524) and a vanadium + nickel content of 70 ppmw, and boiled
below 520C to an extent of 50 %w. Application of relation 4, in
the form:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F i
shows that for optimum utilization of the combination process
care should be taken that the RCT reduction in the catalytic
hydrotreatment is between 54.1 and 64.1%. In the catalytic
20 hydrotreatment of Experiment 66 the space velocity applied was
0.50 g.g 1~h 1 and the RCT reduction achieved was 59%. In the
solvent deasphalting of Experiment 66 an asphaltic bitumen D was
separaæed which had an RCT of 41 %w.
ExReriment 67
-
The feed used in this experiment was a mixture CD obtained
by mixing 100 pbw of atmospheric residue C with 12 pbw of
as~haltic bitumen D obtained in the above Experiment 66.
Application of relation 4 in the form:
maximum RCT reduction = F , and
max
minimum RCT reduction = F
min
shows that for optimum utilization of the combination process
care should be taken that the RCT reduction in the catalytic
hydrotreatment is between 36.5 and 47.7%. In the catalytic
hydrotreatment of Experiment 67 the space velocity used was
35 0.43 g.g 1.h 1 and the RCT reduction achieved was 42.1%. In the
7~
- 45 -
solvent deasphalting an asphaltic bitumen E was separated which
had an RCT of 39 %w.
Experiment 68
I'he feed used in this experiment was a mixture CE obtained
by mixing 100 pbw of atmospheric residue C with 12 pbw of
asphaltic bitumen E obtained in the above Experiment 67.
Application of relation 4 in the form:
maximum RCT reduction = FmaX~ and
minimum RCT reduction = F .
mln
shows that for optimum utilization of the combination process
care should be taken that the RCT reduction in the catalytic
hydrotreatment is between 37.1 and 48.3%. In the catalytic
hydrotreatment of Experiment 68 the space velocity used was
0.43 g.g .h 1 and the RCT reduction achieved was 42.7%. In the
solvent leasphalting an asphaltic bitumen F was separated which
had an RCT of 39 %w. Since the RCT of asphaltic bitumen F is
equal to that of asphaltic bitumen E, this is the moment when in
recycling the asphaltic bitumen the process has reached its
stationary state. The results of Experiments 66~68 are listed in
Table I.
~L8Z77~
- ~i6 -
TABLE I
Experiment No. 66 67 68
Distillatlon
.
Yield of products calculated
on 100 pbw feed, pbw
c4 1.03 0.92 0.93
H2S + NH3 3.2 3.0 3.0
C5 - 370~C 10.5 9.8 9.9
370-520C (vacuum distillate)58.1 51.9 52.0
520C (vacuum residue) 28.9 36.1 35.9
RCT of the vacuum distillate, %w 0.3 0.3 0.3
RCT of the vacuum residue, %w 13.6 18.3 17.9
Deasphalting
Temperature, C 133 135 136
Yield of deasphalted vacuum
residue, pbw 21.8 21.6 21.8
Yield of asphaltic bitumen, pbw 7.1 14.5 14.1
RCT of the deasphalted vacuum
residue, %w 4.8 4.4 4.3
RCT of the asphaltic bitumen, %w 41 39 39
ixing
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 79.9 73.5 73.8
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w 1.5 1~5 1.5
EXAMPLE 5
A heavy mixture AB was used which had been obtained by
mixing 100 pbw of a vacuum residue A and 30 pbw of an asphaltic
't7~3
- 47 -
bitumen B. Vacuum residue A had an RCT of 19 %w (determined
by ASTM method D 524), a vanadium ~ nickel content of 180
ppmw and a 5% boiling point of 520C. Asphaltic bitumen B had an
RCT of 35 %w (calcula~ed from the CCT determined by ASTM method
D 189) and a vanadium ~ nickel content of 110 ppmw. It was
obtained by solvent deasphalting with n butane of a vacuum
residue obtained in the distillation of a hydrotreated mineral
oil vacuum residue.
A catalytic hydrotreatment alone is not sufficient to
prepare from mixture AB an oil having an initial boiling point
of 370C and an RCT of 2.5 %w in view of the maximum permissible
value of G. In addition to the catalytic hydrotreatment, a
solvent deasphalting treatment should be applied. Application of
relation 5, in the form:
maximum RCT reduction - F , and
max
minimum RCT reduction = F
min
shows that for optimum utilization of the combination process
care should be taken that the RCT reduction in the catalytic
hydrotreatment is between 34.0 and 47.0 %w.
The mixture AB was subjected to catalytic hydrotreatment
in eleven experiments to prepare atmospheric residues having an
initial boiling point of 370C and different RCT's (e). The
experiments were similar to those described for Experiments
1-13, the weight ratio between the Ni/V/SiO2 and Co/Mo/Al203
catalysts however being 1:2. The reaction conditions were: a
temperature of 380C, a pressure of 170 bar and a H2/oil ratio
of 1000 Nl/kg, varylng space velocities being used. The results
of Experiments 69-79 at run hour 400 are listed in Table J.
For each experiment the table gives the space velocity
30 used, the RCT reduction (d e x 100) achieved and the
d
corresponding C4 production (calculated as %w on feed).
Experlments 69-78 were carried out in pairs, the difference in
space velocity between the two experiments of each pair being
such as to achieve a difference in RCT reduction of about 1.0%.
77e~
-- l!8 --
The table further gives the C~ production per % RCT reduction
(G) for each pair of experiments.
TABLE J
Experiment Space RCT C4 G,
No. velocity,reduction, production,
-1 -1 %w on feed %w
69 2.95 10.2 0.380 1
~ 0.037
2.69 11.1 0.413 J
71 1.16 22.4 0.832
~ 0.038
72 1.12 23.2 0.860 )
73 0.66 33.5 1.4~0
1 0.056
74 0.63 34.3 1.454 )
0.38 46.8 2.240
~ 0.074
76 0.36 47.7 2.306 )
77 0.23 58.5 3.370
~ 0.125
78 0.22 59.3 3.470 )
79 0.48 40.8 1.800
* RCT reduction = - x 100%
7r7~
- 49 -
Only Experiments 74, 75 and 79 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. As can be seen in Table J in Experiments
69-70 and 71-72, G remains virtually constant (G ). In Experi-
ments 73-74 and 75-769 in which RCT reductions were achieved of
about 34 and 47%, respectively, G was about 1.5 x G and
2.0 x G 7 respectively.
The products obtained in the catalytic hydrotreatment
according to Experiments 71, 77 and 79 were further treated as
hereinbefore described for Experiments 14, 15 and 16. The
results (of which only Experiment 82 is an experiment according
to the invention) are listed in Table K.
77~
- 50 -
TABLE K
Experiment No. 80 81 82
H2-treated product from
Experiment No. 71 77 79
Distillation
Yield of products calculated
on 100 pbw feed, pbw
C4 0.8 3.4 1.8
H2S + NH3 2.2 4.1 3.5
C5 - 370C 8.0 12.8 11.0
370-520DC (vacuum distillate~22.9 32.0 29.4
520C (vacuum residue) 67.2 49.9 55.8
RCT of the vacuum distillate, %w 0.4 0.3 0.3
RCT of the vacuum residue, ~OW 23.5 15.2 20.3
Deasphalting
Temperature, C 134 130 131
Yield of deasphalted vacuum
residue, pbw 30.4 33.9 32.4
Yield of asphaltic bitumen, pbw 36.8 16.0 23.4
RCT of the deasphalted vacuum
residue, %w 4.1 4.6 4.5
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 53.3 65.9 61.8
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w 2.5 2.5 2.5
~ ~ ~Z~7~1
- 51 -
EXAMPLE 6
Three experiments (Experiments 83-85) were carried out with
the object of preparing an oil having an initial boiling point
of 370C ~nd an RCT of 2.5 70W and to investigate the feasibility
of recycle of the asphaltic bitumen produced to the catalytic
hydrotreatment. In the experiments three different residual
feedstocks were subjected to a catalytic hydrotreatment in the
same reactor and applying the same reaction conditions as
described for Experiments 18-30. The products from the catalytic
hydrotreatment were further treated as described for Experiments
14, 15 and 16.
Experiment 83
The feed used in this experiment was the vacuum residue A
of Example 5. Application of relation 5 shows that for optimum
utilization of the combination process care should be taken that
the RCT reduction in the catalytic hydrotreatment is between 52
and 62%. In the catalytic hydrotreatment of Experiment 83 the
space velocity applied was 0.30 g.g .h and the RCT reduction
achieved was 577. In the solvent deasphalting of Experiment 83
an asphaltic bitumen C was separated which had an RCT of 36 70W.
ExReriment 84
The feed used in this experiment was a mixture AC obtained
by mixing 100 pbw of vacuum residue A with 20 pbw of asphaltic
bitumen C obtained in the above Experiment 83. Application of
relation 5 shows that for optimum utilization of the combination
process care should be taken that the RCT reduction in the
catalytic hydrotreatment is between 38.4 and 50.4%. In the
catalytic hydrotreatment of Experiment 84 the space velocity
applied was 0.29 g.g l.h 1 and the RCT reduction achieved was
30 45%. In the solvent deasphalting an asphaltic bitumen D was
separated which had an RCT of 39 70W.
Experiment 85
The feed used in this experiment was a mixture AD obtained
by mixing 100 pbw of vacuum residue A with 20 pbw of asphaltic
35 bitumen D obtained in the above Experiment 84. Application o~
77~
- 52 -
relation 5 shows that for optimum utilization of the combination
process care should be taken that the RCT reduction in the
catalytic hydrotreatment is between 37~8 and 49.8%. In the
catalytic hydrotreatment of Experiment 85 the space velocity
5 applied was 0.28 g.g .h and the RCT reduction achieved was
44%. In the solvent deasphalting an asphaltic bitumen E was
separated which had an RCT of 39 ~w. Since the RCT of asphaltic
bitumen E is equal to that of asphaltic bitumen D, this is the
moment when in recycling the asphaltic bitumen the process has
10 reached its stationary state. The results of Experiments 83-85
are listed in Table ~.
77~
TABLE L
Experiment No. 83 84 85
Distillation
Yield of p~oducts calculated
on 100 pbw feed, pbw
C4 1.70 1.561.58
2 3 4.5 3.9 3.9
C5 - 370C 8.3 7.4 7.2
370-520C (vacuum distillate)34.0 30.129.9
520C* (vacuum residue) 53.0 58.558.7
RCT of the vacuum distillate, %w 0.4 0.4 0.4
RCT of the vacuum residue, %w 13.218.0 18.7
Deasphalting
Temperature, C 133 133 132
Yield of deasphalted vacuum
residue, pbw 38.0 35.134.6
Yield of asphaltic bitumen, pbw 15.023.4 24.1
RCT of the deasphalted vacuum
residue, %w 4.4 4.3 4-3
RCT of the asphaltic bitumen, %w 36 39 39
Mixing
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue~ pbw 72.0 65.264.5
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w 2.5 2.5 2.5
EXAMPLE 7
A heavy mi~ture AB was used which had been obtained by
mixing 100 pbw of an asphaltic bitumen A and 35 pbw of an
asphaltic bitumen B. Asphaltic bitumen A obtained by
7~
- 5~ -
solvent deasphalting with propane of a mineral oil vacuum
residue had an RCT of 25.4 %w (calculated from the CCT
determined by ASTM method D 189), a vanadium ~ nickel content of
250 ppmw and an average molecular weight of 1400. Asphaltic
5 bitumen B had an RCT of ~l0 %w (calculated from the CCT
determined by ASTM method D ]89) and a vanadium ~ nickel content
of 125 ppmw. It was obtained by solvent deasphalting with
n-butane of a vacuum residue obtained in the distillation of a
hydrotreated asphaltic bitumen which latter asphaltic bitumen
10 was obtained by solvent deasphalting of a mineral oil vacuum
residue.
A catalytic hydrotreatment alone is not sufficient to
prepare from mixture AB an oil having an initial boiling pOillt
of 370C and an RCT of 3.0 %w in view of the maximum permissible
15 value of G. In addition to the catalytic hydrotreatment, a
solvent deasphalting treatment should be app].ied. Application of
relation 6 shows that for optimum utilization of the combination
process care should be taken that the RCT reduction in the
catalytic hydrotreatment is between 36.7 and 50.7~O.
The residual feed mixture AB was subjected to catalytic
hydrotreatment in eleven experiments to prepare atmospheric
residues having an initial boiling point of 370C and different
RCT's (e). The experiments were similar to those described for
Experiments 18-30, the weight ratio between the ~i/V/Si02 and
25 Co/Mo/A1203 catalysts however being 1:2. All other reaction
conditions were identical. The results of Experiments 86-96 at
run hour 430 are listed in Table ~.
77~
- 55 -
TABLE M
Experiment Space RCT C4 G,
No.velocity, reduction, production,
g g-l h-l % %w on feed %~
86 1.29 10.2 0.226 ~
~ 0.022
87 1.18 11.1 0.246 J
88 0.62 20.4 0.468
0.023
89 0.60 21.7 0.489
90 0.34 36.3 0.894 ~
0.033
91 0.32 37.4 0.930
92 0.19 50.5 1.427 ~
1 0.044
93 0.18 51.3 1.462 J
94 0.11 65.6 2.295 ~
1 0.072
95 0.10 66.5 2.360 )
96 0.25 43.5 1.150
~ 56 ~
Only Experiments 91 ~ 92 and 96 are experiments according to
the invention. The other experiments have been included for
reasons of comparison. As can be seen in Table M in Experiments
86-87 and 88-89 ~ G remains virtually constant (G ). In Experi~
5 merlts 90-91 and 92-93~ in which RCT reductions were achieved of
about 37 alld 51~o~ respectively, G was about 1~5 x G and
2~ 0 x G , respectively.
The products obtained in the catalytic hydrotreatment
carried out according to Experiments 89 ~ 94 and 96 were further
treated as described hereinbefore for Experiments 14 ~ 15 and 16
The results (of which only E,xperiment 99 is an experiment
according to the invention) are listed in Table N.
77~3
TABLE N
Experiment No. 97 98 99
H2-treated product from
Experiment No. 89 94 96
Distillation
Yield of products calculated
on 100 pbw feed, pbw
C4 0.5 2.3 I.1
H2S + NH3 2~0 4.2 3.5
C5 - 370~C 9.1 14.7 13.2
370-520C (vacuum distillate) 18.2 24.2 22.7
520C+ (vacuum residue) 71.2 57.6 61.3
RCT of the vacuum distillate, %w 0.3 0.3 0.3
RCT of the vacuum residue, V/ow 28.7 14.1 22.5
Temperature, C 131 130 l28
Yield of deasphalted vacuum
residue, pbw 29.4 38.4 34.0
Yield of asphaltic bitumen, pbw 41.8 19.2 27.3
RCT of the deasphalted vacuum
residue, ~/OW 4.7 4.7 4.8
Mixing
Yield of mixture of vacuum
disti.llate and deasphalted
vacuum residue, pbw 47.6 62.6 56.7
Initial boiling point of the
mixture, C 370 370 370
RCT of the mixture, %w . 3.0 3.0 3.0
~&~7~
- 58 -
EXAMPLE 8
-
Two experiments were carried out with the object of
preparing an oil having an initial boiling point of 370C and an
RCT of 3.0 %w and to investigate the feasibility of recycle of
5 the asphaltic bitumen produced to the catalytic hydrotreatment.
In these experiments two different residual feedstocks were
subjected to a catalytic hydrotreatment in a 1000 ml reactor
containing two fixed catalyst beds of a total volume of 600 ml.
The catalyst beds consisted of the same Ni/V/SiO2 and
10 Co/Mo/Al203 catalysts as were used in Example 1, the weight
ratio however being 1:2. The reaction conditions were: a
temperature of 400DC, a pressure of 145 bar and a H2/oil ratio
of 1000 ~l/kg. The products from the catalytic hydrotreatment
were further treated as described for Experiments 14, 15 and 16.
15 Experiment 100
The feed used in this experiment was asphaltic bitumen A of
Example 7. Application of relation 6 shows that for optimum
utilization of the combination process care should be taken that
the RCT reduction in the catalytic hydrotreatmen~ is between
20 51.0 and 61.4%. In the catalytic hydrotreatment of Experiment
100 the space velocity applied was 0.22 g.g 1.h 1 and the RCT
reduction achieved was 56%. In the solvent deasphalting of
Experiment 100 an asphaltic bitumen C was separated which had an
RCT of 36 7OW.
25 Experiment l_
The feed used in this experimene was a mixture AC obtalned
by mixing lO0 pbw of asphaltic bitumen A with 25 pbw of
asphaltic bitumen C obtained in the above Experiment 100.
Application of relation 6 shows that for optimum utilization of
30 the combination process care should be taken that the RCT
reduction in the catalytic hydrotreatment is between 41.0 and
54.0%. In the catalytic hydrotreatment of Experiment 101 the
space velocity applied was 0.21 g.g 1.h 1, and the RCT reduction
achieved was 47.5%. In the solvent deasphalting an asphaltic
35 bitumen D was separated which had an RCT of 36 7OW.
- 59 -
Since the RCT of asphaltic bitumen D is equal to that of
asphal~ic bitumen C, this is the moment when in recycling the
asphaltic bitumen the process has reached its stationary state.
The results of Experiments 100 and 101 are listed in Table 0.
TABLE 0
Experiment No. 100 101
Distil ation
Yield of products calculated
on 100 pbw feed, pbw
C4- 2.22 2.0
H2S + NH3 3.4 2.9
C5 - 370C 17.0 14.4
370-520C (vacuum distillate) 18.4 16.0
520C (vacuum residue) 61.0 66.7
RCT of the vacuum distillate, %w O.l~ 0.4
RCT of the vacuum residue, %w14.5 17.9
Deasphalt in~
Temperature, C 132 133
Yield of deasphalted vacuum
residue, pbw 41. 5 38.O
Yield of asphaltic bitumen~ pbw 19.5 28.7
RCT of the dèasphalted vacuum
residue, %w 4.2 4.1
RCT of the asphaltic bitumen, ~Ow 36 36
Mixing
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 59.9 54.0
Initial boiling point of the
mixture, ~C 370 370
RCT of the mixture, %w 3.0 3.0
7'7~.~
- 60 -
EXAMPLE _
A heavy mixture ABC was used which had been obtained by
mixing 55 pbw of an atmospherlc residue A with 30 pbw of a
vacuum residue B and with 15 pbw of an asphaltic bitumen C.
5 Atmospheric bitumen A which was obtained in the distillation of
a crude mineral oil9 had an RCT of 10 ~OW (determined by ASTM
method 524), a vanadium ~ nickel content of 70 ppmw and a
percentage boiling below 520C of 50 %w. Vacuum residue B which
was obtained in the distillation of a crude mineral oil, had an
10 RCT of 20.6 %w (computed from the CCT determined by ASTM method
D 139)~ a vanadium + nickel content of 170 ppmw and a 5 %w
boiling point of 500C. Asphaltic bitumen C had been obtained in
the deasphalting with propane of a mineral oil vacuum residue.
It had an RCT of 25.4 ~/OW (computed from the CCT determined by
15 ASTM method D 189), an average molecular weight of 1400
(determined by ASTM method D 3592-77, using toluene as the
solvent) and a vanadium + nickel content of 250 ppmw.
The mixture ABC had an RCT of 15.5 %w, a vanadium + nickel
content of 127 ppmw and 29.5 /OW of the mixture boiled below
20 520C.
The mixture ABC with an RCT of 15.5 %w (b) was subjected to
catalytic hydrotreatment in fifteen experiments to prepare
atmospheric residues having an initial boiling point of 370~C
and diferent RCT's ~c). The experiments were similar to those
25 described for Experiments 1-13, the weight ratio between the
Ni/V/SiO2 and Co/Mo/Al2O3 catalysts however being 1:2. The
reaction conditions were: a temperature of 400C, a pressure of
160 bar and a H2/oil ratio of 1500 Nl/kg, varying space
velocities being used. The results of Experiments 102-116 at run
30 hour 250 are listed in Table P.
7P~3
- 61 -
TABLE P
Experiment Space RCT C4 ~,
No. velocity, reduction, production,
K.g l h 1 % %w on feed _%w
102 11.4 10.4 0.166
0.016
103 10.4 11.3 0.181
104 6.05 19.8 0.312 ~
~ 0.016
105 5.62 21.0 0.331 J
106 2.62 39.7 0.652 )
~ 0.017
107 2.53 40.6 0.668 )
108 1.69 50.2 0.836 ~
0 018
109 1.61 51.5 0.859
110 1.13 59.9 1.037 1
~ 0.024
111 1.08 60.9 1.061 )
112 0.70 70.2 1.316 ~
0.032
113 0.67 70.9 1.339
114 0.37 80.1 1.908 1
~ 0.131
115 0.35 81.1 2.039 J
116 0.90 65.0 1.165
7~
- 62 -
Of Experiments 102-116 only Experiments 111, 112 and 116
are experiments according to the invention. The other exyeri-
ments have been included for reasons of comparison. As can be
seen in Table P in Experiments 110-111 and 112-113, in which RCT
5 reductions were achieved of about 60 and 70%, respectively, G
was about 1.5 G and 2.0 Gc, respectively.
The product obtained in the catalytic hydrotreatment
carried out according to Experiment 116 was further separated by
successive atmospheric distillation, vacuum distillation and
10 solvent deasphalting as described hereinbefore. The results are
listed hereinafter.
Z77~
- 63 -
Experiment No. I17
H2-treated product from
Experiment No. 116
Distillation
Yield of products ca]culated
on 100 pbw feed, pbw
C4 1.17
H2S + NH3 2.2
C5 - 370C 13.3
370 520C (vacuum distillate) 47.0
520C+ (vacuum residue) 33.9
RCT of the vacuum distillate, %w 0.5
RCT of the vacuum residue, %w 12.3
Deasphaltin~
Yield of deasphalted vacuum
residue, pbw 27.6
Yield of asphaltic bitumen9 pbw 6.3
RCT of the deasphalted vacuum
residue, %w 5.8
Mixin~
Yield of mixture of vacuum
distillate and deasphalted
vacuum residue, pbw 74.6
Initial boiling point of the
mixture, C 370
RCT of the mixture, %w 2.5
1) solvent = n-butan~
solvent/oil weight ratio = 3:1
temperature, 118C
pressure = 41 bar
