Note: Descriptions are shown in the official language in which they were submitted.
llS~ '7
-- 1 --
PROCESS FOR ~HE PREPARATIO~ OF HYDROCARBO~S A~D
HYDROCARBONS SO PREPARED
The invention relates to a process for the preparation of a
hydrocarbon mixture from a mixture of carbon monoxide and hydrogen
with an H2/CO molar ratio of less than 2.0, using a bifunctional
catalyst combination (I) containing one or more metal components
with catalytic activity for the conversion of an H2/CO mixture
into acyclic hydrocarbons and/or acyclic oxygen-containing hydro-
carbons and a crystalline silicate having the capability of
catalyzing the conversion of acyclic hydrocarbons and acyclic
oxygen-containing hydrocarbons into aromatic hydrocarbons, on the
understanding that if the H2/CO mixture has an H2/CO molar ratio
below 1.5, use is made of a trifunctional catalyst combination
containine one or more metal components with catalytic activity
for the conversion of an H2/CO mixture into acyclic hydrocarbons
and/or acyclic oxygen-containing hydrocarbons, one or more metal
components with catalytic activity for the conversion of an
H2/CO mixture into an H2/C02 mixture and a crystalline silicate
having the capability of catalyzing the conversion of acyclic
; hydrocarbons and acyclic oxygen-containing hydrocarbons into
aromatic hydrocarbons. Said crystalline silicates are charac-
terized in that they have the followine properties after one
hour's calcination in air at 500C:
a) an X-ray powder diffraction pattern showing as strongest
lines the 4 lines 3tated in ~able A:
TABLE A
d(~)Relative intensity
11.1 + 0.2 VS
10.0 + 0.2 VS
: 3.o4 + 0.07 S
3.72 + o.o6 s
wherein the letters used have the following meaning:
VS = very strong, S = strong, and
. .
. . .
~b~ in the formula which represents the composition of the silicate, ex-
pressed in moles of the oxides, and in which, in addition to oxides
of hydrogen, alkali metal and/or alkaline-earth metal and silicon,
there is present one or more oxides of a trivalent metal A se]ected
from the group formed by aluminium, iron, gallium, rhodium, chromium
and scandium, the A2O3/SiO2 molar ratio (for ~he sake of brevity
further designated m in this patent application) is less than 0.1.
In an investigation by the Applicant concerning this process it was
found that it has two drawbacks. In the first place, when using space velocities
acceptable in actual practice, the conversion of H2/C0 mixture is found to be un-
satisfactory. Further, the process yields a product substantially consisting of
hydrocarbons with at most 12 carbon atoms in the molecule and only very few
hydrocarbons with more than 12 carbon atoms in the molecule.
Further investigation by the Applicant concerning this process has
shown that the two above-mentioned drawbacks can be obviated by giving the
reaction product, or at least its C2 fraction, an after-treatment by contacting
it with a catalyst containing one or more metal components with catalytic
activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons,
which metal components have been selected from the group formed by Ni, Co and Ru,
on the understanding that if the feed for the second step has an H2/C0 molar
ratio of less than 1.5, water is added to this feed and that in the second step
a bifunctional catalyst combination ~II) is used, whic}l contaiTIs! in addition to
metal components with catalytic activity for the convcrsion of an l12/C0 mixture
into acyclic hydrocarbons, also one or more metal components with catalytic
actiuity for the conversion of an H20/C0 mixture into an H2/C02 mixture. In
this way it is achieved that
.
~ - 2 -
~1~4~3~ t
when using space velocities acceptable in actual practice, not only a very
high conversion of the ll2/C0 mixture is obtained, but also that the reaction
product consists substantially of hydrocarbons with more than 12 carbon atoms
in the molecule.
The present invention therefore relates to a process for the
preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and
hydrogen with an H2/C0 molar ratio of less than 2.0 is contacted in a first step
with a bifunctional catalyst combination (I~ as defined above, on the under-
standing that if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5,
a trifunctional catalyst com~ination as defined above is used, at least the
C2 fraction of the reaction product from the first step being contacted in
a second step with a monofunctional catalyst as defined above, on the under-
standing that, if the feed for the second step has- an H2/C0 molar ratio of less
than 1.5, water is added to this feed and that in the second step a bifunctional
catalyst combination (II) as defined above is used.
The Canadian patent application 354,626 filed on 6th August, 1979,
relates to a process for the preparation of a hydrocarbon mixtureJ in which a
mixture of carbon monoxide and hydrogen w~th an H2/C0 molar ratio of less than
1.0 i5 contacted in a first step with a trif~mctional catalyst combination as
defined above and in which at least the C2 fraction of the reaction product
from the first step i5 contacted in a second step with a monofunctional catalyst
as defined a~ove, on the understand~ng that, if t}le feed For the second step
has an H2/C0 molar ratio of less than 1.5, water is adcled to this feed and that
in the second step a bifunctional catalyst com~ination (II) as defined above
is used.
The present patent application thereore relates to a process for the
preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and
' hydrogen with an H2/CO molar ratio of 1,0-2.0 is contacted in a first step with
- 3 -
~:15g~5)~7
a bifunctional catalyst combination ~I~ as defined above, on the understanding
that, if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5, a tri-
functional catalyst combination as defined above is used, and in which at least
the C2 fraction of the reaction product from the first step is contacted in a
second step with a monofunctional catalyst as defined above, on the understanding
that, if the feed for the second step has an H2/C0 molar ratio of less than 1.5,water is added to this feed and that in the second step a bifunctional catalyst
combination (II~ as defined above is used.
In the process according to the invention the starting material is
an H2/C0 mixture with an H2/C0 molar ratio of less than 2Ø Such H2/C0 mixturescan very suitably be prepared by steam gasification of a carbon-containing
material. Examples of such materials are brown coal, anthracite, coke, crude
mineral oil and fractions thereof and oils~ extracted from tar sand and bituminous
; shale~ The steam gasification is preferably carried out at a temperature of
900 - 1500C and a pressure of 10 - 100 bar. In the process according to the
invention it is preferred to start from an H2/C0 mixture with an H2/CO molar
ratio of more than 0.25.
The bi- and trifunct~onal catalyst combinations used in the process
according to the invention in the first step contain, in addition to the metal
components with catalytic activity, a crystalline metal silicate characterized by
the properties mentioned under (a~-~b). Although, in principle the silicates
may contain several metals selected from the group formed by altmlinium, iron,
gallium, rhodium, chromium and scandium, :it i5 pr0ferred or the process accord-
ing to the invention to use catalysts in which the silicate contains only one ofthese metals and in particular silicates which contain as the metal aluminium,
iron or gallium. As regards the presence of aluminium in the silicates, the
follo~ing remarks shQuld be made. The silicon compounds, which from an economic
point of vie~ are su~table for the preparation of crystalline silicates on a
technical scale, contain as a rule a small amount of aluminium as contaminant.
' ~3
-- 4 --
.
.'
~L~S4~
Usually, this aluminium is found, at least partly, in the silicate
prepared~ This means that, if the aim is to prepare for use in the
bi- and trifunctional catalyst combinations a crystalline silicate
containing one or more of the metals iron, gallium, rhodium,
chromium and scandium, whilst the starting material is a base
mixture in which a silicon compound contaminated with aluminium
has been incorporated, as a rule a crystalline silicate will be
obtained containing a slight amount of aluminium.
The crystalline silicates used in the bi- and trifunctional
catalyst combinations should have a value for m which is less
than 0.~. It is preferred to use crystalline silicates for which
m is greater than 0.001 and in particular greater than 0.002 and
silicates ~or which m is smaller than 0.05. If in the process
according to the invention use is made of a bi- or trifunctional
catalyst combination in which a crystalline aluminium silicate
is present for which m is greater than 0.005, it is preferred to
choose for this purpose an aluminium silicate which contains 0.1-
10 %w of one of the elements selected from the group formed by
manganese, calcium, magnesium and titanium, in particular manganese.
The crystalline silicate used in the bi- and trifunctional
catalyst combinations has been defined, inter alia, with reference
to the X-ray powder diffraction pattern. This X-ray powder
diffraction pattern should contain, as strongest lines, the four
lines shown in Table A. The complete X-ray powder diffraction
pattern of a typical example of a silicate suitable for use accord-
ing to the invention is shown in Table B:
3L~ 4~7
-- 6 --
Table B
d(~) Relative intensity d(~)Relative intensity
. . . _
11.1 loo 4.oo 3
.o 70 3.8457
8.93 1 3.7231
7.99 ~ 3.64lo
7.42 1 3.41~ 5
6.68 7 3.34 3
6.35 11 3.30 5
5.97 ~8 3.25 2
5.70 ? 3.05 5
5.56 10 2.9812
5.35 2 2.96 3
4.98 6 2.86 2
4.60 4 2.73 2
4-35 5 2.60 2
4.25 7 2.48 3
4.o7 2 2.40 2
~'
~: ~he crystalline silicates used in the bi- and trifunctional
catalyst combinations can be prepared starting from an aqueous
mixture containing the following compounds: one or more compounds
of an alkali metal or alkaline-earth metal (M), one or more com-
5 pounds containing an organic cation (R) or from which such a cation
is formed during the preparation of the silicate, one or more
silicon compounds and one or more compounds in which a tri~alent
metal A selected from the group ~ormed by alumlnium, iron, gallium,
rhodium, chromium and scandium is present,. The preparation is
10 performed by maintaining the mixture at elevated temperature until
the silicate has been formed and subsequently separating the crystals
of the silicate from the mother liquor and calcining them. In the
aqueous mixture from which the silicates are prepared the various
compounds should be present in the ~ollowing ratio, expressed in
`j 15 moles of the oxides:
-, ~ .
1~5~
M2/nO : R20 = 0.1 - 20,
R20 : SiO2 = 0.01 - 0.5,
SiO2 : A203 10, and
H20 : SiO2 = 5 - 50; (n is the valency of M)
In the preparation of the silicates it is preferred to start from a
base mixture in which M is present in an alkali metal compound and R in a tetra-
alkylammonium compound and in particular from a base mixture in which ~ is
present in a sodium compound and R in a tetrapropylammonium compound. The
crystalline silicates prepared as described above contain alkali metal ions
and/or alkaline-earth metal ions. They can be replaced By other cations such
as hydrogen ions or ammonium ions by using suitable exchange methods. The
crystalline silicates used in the bi~ and trifunctional catalyst combinations
preferably have an alkali metal content of less than 0.1 ~Ow and in particular
less than 0.05 ~OW.
Although the trifunctional catalyst combinations are described in
this patent application as catalyst combinations containing one or more metal
components with catalytic activity for the conversion of an H2/C0 mixture into
acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons and one or
more metal components ~ith catalytic activity for the conversion of an H20/C0
mixture into an H2/C02 mixture, this does not mean at all that separate metal
components that each have one of the two catalytic functions should always be
present in the trifunctional catalyst combinations. For, it has been found that
metal components and combinations of metal compon0nts with catalytic activity
for the conversion of an H2/C0 mixture into substantially acyclic oxygen-contain-
ing hydrocarbons often also have sufficient catalytic activity for the conversion
of an H20/CO mixture into an H2/CO2 mixture, so that incorpor~tion of one metal
component or one combination of metal components into the trifunctional catalyst
,.~ .
,
~54t)3~
combinations will then usually suffice. Metal components and combinations of
metal components with catalytic activity for the conversion of an H2/CO
mixture into substantially acyclic hydrocarbons) usually have no or
insufficient activity for the conversion of an H20/CO mixture into an H2/C02
mixture. When using such metal components or
- 7A -
`` ~l1~4~J~'7
combinations of metal components in the trifunctional catalyst com-
binations, one or more separate metal components with catalytic
activity for the conversion of an H20/C0 mixture into an H2/C02
- mixture should therefore in most cases be incorporated into these
5 metal components.
The bi- and trif mctional catalyst combinations used in the
first step of the process according to the invention are preferably
composed of two or three separate catalysts, which will, for con-
venience, be designated catalysts X, Y and Z. Catalyst X is the one
10 containing the metal components having catalytic activity for the
conversion of an H2/C0 mixture into acyclic hydrocarbons and/or
acyclic oxygen-containing hydrocarbons. Catalyst Y is the
crystalline silicate. Catalyst Z is the one containing the metal
components having catalytic activity for the conversion of an
15 H20/C0 mixture into an H2/C02 mixture. As has been explained here-
inbefore the use of a Z-catalyst may in some cases be omitted for
the trifunctional catalyst combinations.
If as the X-catalyst a catalyst is used which is capable of
converting an H2/C0 mixture into substantially acyclic oxygen-
20 containing hydrocarbons, preference is given to a catalyst whichis capable of converting an H2/C0 mixture into substantially
`- methanol and/or dimethyl ether. Very suitable catalysts for this
purpose are ZnO-Cr203 compositions, in particular such compoæitions
in which the atomic percentage of zinc, based on the sum of zinc
25 and chromium, is at least 60% - 80~. When using a ZnO-Cr203
composition as X-catalyst, the use of a Z-catalyst may be omitted
for the trifunctional catalyst combinations.
X-catalysts which are capable of converting an H2/C0 mixture
into substantially acyclic hydrocarbons are referred to in the
30 literature as Fischer-Tropach catalysts. ~uch catalysts contain
one or more metals from the iron group or ruthenium together with
one or more promotera to increase the activity and/or selectivity
and sometimes a carrier material such as kieselguhr. If in the
.
~, ,,~,
'7
first step of the process according to the invention use is made
of a bi- or trifunctional catalyst combination in which the X-
catalyst is a Fischer-Tropsch catalyst, it is preferred to choose
~or this purpose an iron or cobalt cat~yst~ in particular such a
catalyst which has been prepared by impregnation. Very sui-table
catalysts for this purpose are:
(a~ Catalysts that contain 30-75 pbw iron and 5-40 pbw magnesiumfor 100 pbw alumina and which have been prepared by impregnating
an alumina carrier with one or more ~ueouss~utions of salts
of iron and of magnesium followed by drying the compostion,
calcining it at a temperature of 700-~ 200 C and reducing it.
: Particular preference is given to such catalysts that contain,
in addition to 40-60 pbw iron and 7.5-30 pbw magnesium, 0.5-5
pbw copper as the reduction promoter and ~-5 pbw potassium as
the selectivity promoter per 100 pbw alumina, and which have
been calcined at 750-850 C and reduced at 250 -350 C.
(b~ Catalysts that contain ~0-40 pbw iron and 0.25-10 pbw
chromium per 100 pbw silica and which have been prepared
by impregnating a silica carrier with one or more aqueous
solutions of salts of iron and of chromium, followed by
drying the composition, calcining it and reducing it at a
temperature of 350-750C. Particular preference is given
to such catalysts which contain, in addition to 20-35 pbw
iron and o.5-5 pbw chromium, 1-5 pbw potassium as the
selectivity promoter and which have been calcined at 350-
700 C and reduced at 350-500C.
(c~ Catalysts that contain 10-40 pbw cobalt and 0. 25-5 pbw
zirconium, titanium or chromium per 100 pbw silica and
which have been prepared by impregnatin~ a silica carrier
with one or more aqueous solutions of salts of cobalt and
zirconium, titanium or chromium followed by drying the
CQmpOsition~ calcining it at 350-700 C and reducing it at
200-350C .
When using the iron catalysts mentioned under (a~ and (b)
35 as X-catalyst, the use of a Z-catalyst can be omitted. When
using the cobalt catalysts mentioned under ~c~ as X-catalyst, a
1~540;~
-- ~o
Z-catal~st should also be incorporated into the trifunctional
catalyst combinations. If in the first step of the process
accord;ng to the invention use is made of a bi- or trifunctional
catalyst combination in which catalyst X is a Fischer-Tropsch
catalyst, it is preferred to choose for this purpose an iron
catalyst as described under (a~ and (b).
Z-catalysts which are capable of converting an H20/CO ~ixture
into H2/C02 mixture are referred to in ~he literature as C0-shift
catalysts.
In the bi- and trifunctional catalyst combinations the
catalysts X,Y and, optionally, Z are preferably present as a
physical mixture. When carrying out the first step of the
process, using a fixed catalyst bed, this bed may also be built
up of alternate layers of particles of the catalysts X, Y and,
optionally, Z.
The first step of the process according to the invention
can very suitably be carried out by conducting the feed in
upward or in downward direction through a vertically mounted
reactor in which a fixed or moving bed of the bi- or trifunction-
al catalyst combination is present. ~he first step may, for
instance, be carried out in the so-called fixed-bed operation,
in bunker-flow operation, in ebullated-bed operation or fluidi~ed-
bed operation. ~he first step of the process is preferably
carried out under the following conditions: a temperature of
; 25 200-500C and in particular 250-450C, a pressure of 1-150 bar
and in particular of 5-100 bar and a space velocity of 50~5000
and in particular of 300-3000 Nl gas/l catalyst/h.
In the process according to the invention at least the
C2 fraction of the reaction product from the first step i8
3 used as the feed for the second step. Instead of the C2
fraction of the reaction product from the first step, a
different fraction of this product, e.g. the C4 fraction,
or even the whole product from the first step, ma~ be used -
if desired - as the feed for the second step. In the second
step of the process according to the invention it is intended
to convert as much as possible of the C0 present in the feed
for the second step into acyclic hydrocarbons over a monofunction-
al catalyst containing one or more metal components with catalytic
activity for the conversion of an H2/C0 mixture into acyclic hydro-
carbons, which metal components have been selected from the group
5 formed by cobalt, nickel and ruthenium. To this end the H2/C0 molar
ratio in the feed for the second step should be at least 1.5 and
preferably 1.75-2.25. When using an H2/C0 mixture with a high H2/C0
molar ratio as the feed for the first step, the process according
to the invention can yield a reaction product from the first step,
lO which has an H2/C0 molar ratio of at least 1.5, which is suitable,
as such, to be converted in the second step over the said catalyst.
An attractive way of ensuring in the process according to the
invention that the reaction product from the first step has an H2/C0
molar ratio of at least 1.5 is adding water to the feed for the
15 first step and the use of a trifunctional catalyst combination in
the first step. Under the influence of the catalyst combination
present in the first step this water reacts with C0 from the feed
to form an H2/C02 mixture. A further advantage of the addition of
water to the feed of the first step in the process according to
20 thè invention is that it increases the stability of the trifunctional
catalyst combination. Water addition to the feed for the first step,
and a trifunctional catalyst combination can be applied in the
process according to the invention both in cases where withou-t
water addition the first step would have given a reaction
25 product with an H2/C0 molar ratio of less than 1.5, and in cases
where, also without water addition, the first step would have
given a reaction product with an H2/C0 molar ratio of at least 1.5,
but where it is desirable tha-t the feed which is contacted with the
catalyst in the second step has a higher H2/C0 molar ratio. If in the
30 process accordin~ to the invention an embodiment is chosen in which
water i6 added to the ~eed ~or the first step, and a tri~unctional
catalyst combination is used , the amount of water required is
substantially determined by the H2~C0 molar ratio of the feed for
the first step, the activity of the trifunctional catalyst
35 combination in the first step for converting an H23/C0 mixture
into an H2fC02mixture and the desired H2/C0 molar ratio of the
~15~7
reaction product of the first step.
If in the process according vo the invention a reaction
roduct is obtained from the first step with an H2~C0 molar ratio
of less than 1.5, after water addition to the feed for the f;rst
step or not and using a trifunctional catalyst combination, water
should be added to the feed for the second step and in the second
step a bifunctional catalyst combination (II) should be incorporated,
which contains, in addition to the metal components with catalytic
activity for the conversion of an ~2/C0 mixture into acyclic hydro-
10 carbons~ also one or more metal components with catalytic activityfor the conversion of an H20/C0 mixture into an ~2/C02 mixture.
The bifunctional catalyst combinations which are optionally used in
the second step of the process according to the invention, are
preferably composed of two separate catalysts, which will, for con-
15 venience, be designated catalyst A and catalyst B. Catalyst A is theone containing the metal components having catalytic activity for the
conversion of an X2/C0 mixture in~o acyclic hydrocarbons, and which
metal components have been selected from the group formed by cobalt,
nickel and ruthenium. Catalyst B is the one containing the metal
20 components having catalytic activity for the conversion of an H2Q/
C0 mixture into an H2/C02 mixture. Both when using a monofunctional
; catalyst and when using a bifunctional catalyst combination in the
second step of the process according to the invention, preference
is given to a cobalt catalyst as the A-catalyst and in particular
25 to a cobalt catalyst prepared by impregnation. Very suitable catalysts
for this purpose are the cobalt catalysts described hereinbefore under
(c~. Suitable B-catalysts are the usual C0-shift catalysts. In the
bifunctional catalyst combinations (II) catalysts A and B may be
present as a physical mixture. When the second step of the process
30 is carried out using a fixed catalyst bed~ this bed is pre~erably
built up of two or more alternate layers of particles of, success-
ively, catalyst B and catalyst A. Water addition to the feed for the
second step together with the use of a bifunctional catalyst com-
bination in tke second step can be used in the process according ~G
35 the invention both in cases where the reaction product from the first
step has an H2/C0 molar ratio of less than 1.5, and in cases where
. .
- ~3 -
the reaction product f`rom the ~irst step already has an ~2/CO molar
ratio o~ at least ~.5, but where it is desirable that the feed which
is contacted with catal~st A in the second step should have a higher
H2/CO molar ratio. If in the process according to the invention an
5 embodiment is chosen in which water is added to the feed for the
second step together with the use of a bifunctional catal~st com-
bination in the second step, the amount of water required is sub-
stantially determined by the ~2/CO molar ratio of the feed for the
second step, the activity of the catalyst combination for the con-
lO version of an H20/CO mixture into an H2/C02 mixture and the desiredH2/CO molar ratio of the product that is contacted with catalyst A.
The second step of the process according to the invention can
very eonveniently be carried out by conducting the feed in upward or
in downward direction through a vertieally mounted reactor in which
15 a fixed bed of the monofunctional catalyst or of the bifunctional
catalyst combination is present. The second step of the process can
also be carried out using a suspension of the catalyst or catalyst
combination in a hydrocarbon oil. The second step of the process is
preferably earried out under the f`ollowing conditions: a temperature
20 of 125-350C and in partie~lar of 175-275C and a pressure of 1-150
bar and in particular of 5-100 bar.
The invention will now be explained with reference to the
following example:
Exam~le
The following catalysts were used in the investigation:
Catalyst 1
A Co/Zr/SiOz catalyst that contained 25 pbw cobalt and 1.8 pbw
zirconium per ~00 pbw silica and which had been prepared ~y
impregnating a siliea earrier with an aqueous solution containing
30 a eobalt and a zireonium salt, rollowed by drying the eomposition,
calcining it at 500 C and reducing it at 280C.
Catalyst 2
An Fe/Mg/Cu/K/Al~03 catalyst that contained 50 pbw iron,20 pbw
magnesium, 2.5 pbw copper and 4 pbw potassium per 100 pbw alumina
35 and which had been prepared by impregnating an alumina carrier with
an aqueous solution containing an iron, a magnesium, a copper and a
_ ~4 -
potassium salt, follo~ed by dr~ing the composition, calcining it at
800 C and reducing it at 325 C.
Catal~st 3
An Fe/Cu/K/SiO2 catalyst that contained 25 pbw iron, 1.25 pbw copper
and 2 pbw potassium per 100 pbw silica and which had been prepared
by impregnating a silica carrier with an aqueous solution containing
an iron, a copper and a potassium salt, ~ollowed by drying the
composition, calcining it at 400C and reducing it at 280C.
Catalyst 4
lO A Cu/Zn/A1203 catalyst with a Cu/Zn atomic ratio of 0.55.
Catalyst 5
A ZnO-Cr203 catalyst in which the atomic percentage of zinc based
on the sum of zinc and chromium was 70%.
CatPlysts 6-8
Three crystalline silicates (silicates A-C) were prepared by heating
mixtures of SiO2, NaOH, CC3H7)4~ OH and either NaAlO2, or Fe(N03)3,
or Ga(N03)3 in water for six hours at 150 C in an autoclaue under
autogenous pressure. After the reaction mixtures had cooled down,
the silicates formed were filtered off, washed with water until the
20 pH of the wash water was about 8, dried at 120 C and calcined at
500C.
The silicates A-C had the following properties:
(a) thermally stable up to a temperature above 800C,
(b) an X-ray powder diffraction pattern substantially equ~l to the
one given in Table B,
(c) a value for m as mentioned below:
silicate A: A1203/SiO2 molar ratio = 0.0133,
silicate B: Fe203/SiO2 molar ratio = 0.0050,
silicate C: Ga203/SiO2 mol~r ratio 5 o.oo83.
The molar composition of the a~ueous mixtures from which the
silicates A-C were prepared can be represented as follows:
Silicate A:
1 Na20 .4.5 ~C3H7)4N120. 0.33 Al203. 25 SiO2 .450 H20
Silicate B:
2 ~ 3 7) 4~ 2 o 125 Fe203 .25 ~iO2~ 468 EI O
.
J
Silicate C:
2 4-5 [(C3x7)4~ 2Q 0-22 Ga2o3 25 Sio2.450 H20.
The silicates D-F were prepared from the silicates A-C,
respectively, by boiling the silicates A-C with ~.0 molar NH4~03
solution, washing with water, boiling again with ~.0 molar NH4N03
solution and washing, drying and calcining. A catalyst 6 was pre-
pared from silicate D by impregnating silicate D with an aqueous
solution of a manganese salt followed by drying the composition
and calcining it. Catalyst 6 contained 3%w manganese.
Silicates E and F were used as such as catalyst 7 and catalyst 8,
respectively.
Cata yst mixtures I-VI
- Six catalyst mixtures were prepared. The catalyst mixtures I-V
consisted each of a physical mixture of two of the above-mentioned
catalysts in the following ratio:
Cat. mixture I = 2 pbv of cat. 5 + 1 pbv of cat. 6,
Cat. mixture II = 2 pbv of cat. 5 + 1 pbv of cat. 7,
Cat. mixture III= 2 pbv of cat. 5 + 1 pbv of cat. 8,
Cat. mixture IV = 2.5 pbv of cat. 2 + 1 pbv of cat. 6,
20 Cat. mixture V = 2 pbv of cat. 3 + 1 pbv of cat. 7.
Catalyst mixture VI consisted of a layer of catalyst 4
; and a layer of catalyst 1 in a volume ratio of 1:2.
The catalyst mixtures I-VI and catalyst 1 were tested for the
preparation in one or two steps of a hydrocarbon mixture from an
H2/C0 mixture. The test was carried out in ~e.or two reactors
of 50 ml each, in which a fixed catalyst bed was present.
Twenty-three experiments were carried out. The experiments
1,4,7,10,15,17,19 and 22 were carried out in one step; the other
experiments in two steps. In all the exEeriments, with the exception
o~ experiments 14,22 and 23, a temperature of 375C was used in the
~irst step. In experiment 14 the temperature in the first step was
280C and in the experiments 22 and 23 the temperature in the first
step was 250C.
:
'7
- ~6 -
In all the experiments carried out in two steps the temperature
in the second step was 220 C. In all the experiments, with the
exception o~ experiments 14,22 and 23, a pressure of 60 bar was
used. In OEperi~ents ~4,22 and 23 the pressure was 30 bar.
In the experi~ents 1,4,7 and 10 the space velocity was ~OOQ Nl.l
h . In the experiments ~5,~7,~9 and 22 the space velocity was 50Q
Nl.l -1.h . In all the experiments carrîed out in two steps
the space velocity, based on the sum of the total catalyst system
(in the first & second step~ was 500 Nl.l. .h . In the experiments
6,9, and 12 the C4 fraction of the product from the first step was
used as the feed for the second step. In the remainine experiments
which were carried out in two steps, the total reaction product ~rom
the first step was used as the feed for the second step. The results
of the experiments are stated in Table C.
~ .
,
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~L154~'7
1 7
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N H ~ ~ I
H ~ O ~ N ;--
L
H Lr~ ~t N ~ 1~
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H
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.. . .. .
~154~3'7
Of the experiments listed in the table, only the two-step experiments 3, 6,
9, 12, 13, 14, 16, 18, 20, 21 and 23 are experiments according to the invention.
The one-step experiments 1, 4, 7, 10, 15, 17, 19 and 22 and the two-step
experiments 2, 5, 8 and 11 are outside the scope of the invention. They have
been included in the patent application for comparison. Of the two-step
experiments 3, 6, 9, 12, 13, 14, 16, 18, 20, 21 and 23 only the experiments
16, 18, 20, 21 and 23 are experiments according to the present patent application.
The two-step experiments 3, 6, 9, 12, 13 and 14 are experiments according to
the Canadian patent application 354,626,
10 The advantages of the two-step process according to the invention
as regards the conversion of the H2/C0 mixture and the composition of the
reaction product are evident when the results of the following experiments
are compared
Experiments 3 with experiments 1 and 2
" 6 " " 4 and 5
" 9 " " 7 and 8
" 12 and 13 " " 10 and 11
" 16 " " 15
" 18 " " 17
" 20 and 21 " " 19
; " 23 " " 22
~ - 20 -
.~
