Note: Descriptions are shown in the official language in which they were submitted.
- ~19~3451
-- 1 --
PROCESS FOR THE PROD~CTION OF HYDROCARBO~S
The invention relates to a process for the production of
hydrocarbons from a mixture of carbon monoxide and hydrogen, using
a catalyst combination containing one or more metal components
with catalytic activity for the conversion of an H2/CO mixture
5 into acyclic hydrocarbons and a carrier consisting of a
crystalline silicate zeolite having, in dehydrated form, the
following overall composition, expressed in moles of the oxides
(l.O ' 0.3) (R)2/nO./a Me203/.y(d SiO2 + e GeO2), where
R = one or more mono- or bivalent cations,
Me = at leastone trivalent metal
O ~ a ~ 1
y ~ 12
d 3 0.1,
e 3 O,
d + e = 1, and
n = the valency of R,
and having an ~-ray powder diffraction pattern showing, inter
alia, the reflections given in Table A.
Table A
20 2~ Relative intensity
7.8 - 8.2 S
8.7 - 9.1
11.8 - 12.1 W
12.4 - 12.7 W
25 14.6 - 14.9 W
15.4 - 15.7 W
15.8 - 16.1 W
17.6 - 17.9 W
19.2 - 19.5 W
30 20.2 - 20.6 W
20.7 - 21.1 W
23.1 - 23.4 VS
~J
1198~5~
23.8 - 24.1 S
24.2 - 24.8
29.7 - 30.1 M
The values given in Table A have been determined according to
5 standard methods. Radiation: Cu-K, wavelength: 0.15418 nm. The
letters in Table A used to indicate the relative intensities have
the following meanings: VS = very strong; S = strong; M =
moderate; W = weak; 0 = angle according to Bragg's law.
The complete X-ray powder diffraction pattern of a silicate
10 to be used in the process according to the invention is given in
Table B. (Radiation: Cu-K, wavelength: 0.15418 nm).
Table B
29 Relative intensity description of
(100. I/Io) the reflection
8.00 55 SP
8.90 36 SP
9.10 20 SR
11.95 7 NL
12.55 3 NL
13.25 4 NL
13.95 10 NL
14.75 9 BD
15.55 7 BD
15.95 9 BD
17.?5 5 BD
19.35 6 NL
20.40 9 NL
20.90 10 NL
21.80 4 NL
22.25 8 NL
23.25 100* SP
23.95 45 SP
24.40 27 SP
~A
11984S~
-- 3 --
25.90 11 BD
26.70 9 BD
27.50 4 NL
29.30 7 NL
29.90 11 BD
31.25 2 NL
32.75 4 NL
NL
36.05 5 BD
BD
45 30 9 BD
* lo = intensity of the strongest separated reflection occurring
in the pattern.
The letters in Table B used to describe the reflections have
the following meanings: SP = sharp; SR = shoulder; NL = normal; BD
= broad; ~ = angle according to Bragg's law.
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 the H2/C0 mixture is unsatisfactory. Further, the
process yields a product substantially consisting of hydrocarbons
with less than 5 carbon atoms in the molecule and too few
hydrocarbons with 5-12 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 preparing the catalyst used by ion-exchange i.e. by
contacting the feed 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 are
preferably chosen from the group formed by Fe, Ni, Co, and Ru, and
which component(s) is/are deposited in the crystalline zeolite by
ionexchange. In this manner it is not only achieved that, when
using space velocities acceptable in actual practice, a higher
conversion of the H2/C0 mixture is obtained, but moreover that the
~98~S~
reaction product consists predominantly of hydrocarbons with 5-12
carbon atoms in the molecule.
The present application therefore relates to a process for
the production of hydrocarbons, from a mixture of carbon monoxide
and hydrogen, using a catalyst combination containing one or more
metal components with catalytic activity for the conversion of an
H2/C0 mixture into acyclic hydrocarbons and a carrier, consisting
of a crystalline silicate zeolite having a dehydrated form, the
following overall composition, expressed in moles of the oxides
(1.0 ~ 0.3)(R)2/nO./ a Me203/.
y(d SiO2 + e GeO2), where
R = one or more mono- or bivalent cations,
Me = at least one trivalent metal
l >a ~0,
y ~12,
d ~0.1,
e 30,
d + e - 1, and
n = the valency of R
and having an X-ray powder diffraction pattern showing, inter
alia, the reflections given in Table A, characterized in that, the
metal component(s) has (have) been combined with the carrier by
ion-exchange followed by washing, drying and calcining.
In the process according to the invention the starting
material is an H2/C0 mixture. Such H2/C0 mixtures can very suit-
ably be prepared by steam gasification or partial combustion of a
carbon containing material. Examples of such materials are wood,
peat, brown coal, bituminous coal, anthracite, coke, crude mineral
oil and fractions thereof as well as tars and oils extracted from
tar sand and bituminous shale. The steam gasification or partial
combustion is preferably carried out at a temperature of 900-
1600C and a pressure of 10-100 bar. In the process according to
the invention it is preferred to start from an H2/CO mixture with
an H2/C0 molar ratio of more than 0.25 and less than 6.
~984~1
The catalyst comblnations used in the process according to the inven~
tion contain~ ~n add~ti~on to metql comp~nents ~$th catalytic activity for hydro-
carbon synthesis, at least one crystalline silicate, preferably belonging to the
"Pentasil" group of crystalline silicates. These silicates are described in
the "Atlas of zeolite structure Types" by W.M. Meier and D~H. 01son (1978),
Polycrystal Book Service, Pittsburgh, Pa,, and by E M. Flaninger, J.M Bennet~
R.M. Grose, J.P, Cohen and J.V. Smith, Nature (London), 1978, 271, p 512 and by
L.V.C, Rees, "Proceedings of the Fifth International Conference on Zeolites",
(Naples), 2-6 June, 1980, p 562.
Particularly suitable silicates for the process according to the inven-
tion is the crystalline "Silicalite" mentioned in U.S. patent specification No.
4,061,724 and the crystalline aluminosilicate ZSM-5, which is described in U.S
patent specification No. 3,702,886. Other preferred carriers for the catalyst
to be used in the process according to the invention are a crystalline iron
silicate (CIS) (which has been described in British patent specification No
1,555,928 and U.S. patent specification No. 4,208,305), a crystalline gallium
silicate (Canadian patent No. 1,141,779), and a crystalline cobalt silicate
(Canadian patent application No. 398,341).
In Canadian patent No. 1,142,159 a further crystalline silicate is
described which is very suitable as a catalyst carrier in the process according
to the invention. This silicate has the following composition expressed in
moles of oxides:
p (0 9 + 0-3) M2~n-P (aX23 2 3
Si02 in which M = H and/or alkali and/or alkaline earth metal;
X = Rh, Cr and/or Sc;
Y = Al, Fe and/or Ga;
a ~ 0.5; b ~ 0; a + b = 1;
0 < p ~ 1; n = valency of M.
-- 5
~ lL19~3~5~
The catalyst combinations used in the process according to
the invention contain one or more metal com?onents with catalytic
activity for the conversion of an H2/CO mixture into acyclic
hydrocarbons.
Catalyst components capable of converting an H2/CO mixture
into mainly acyclic hydrocarbons are known in the literature as
Fischer- Tropsch catalyst. Such catalyst components comprise one
or more metals of the iron group or ruthenium together, optionally
with one or more promoters to increase the activity and/or selec-
10 tivity. Suitable catalysts contain 0.1-10% by weight of ruthenium
and/or 0.05-10~ by weight of one or more metals of the iron group
together with one or more promoters in a quantity of 1-50% of the
quantity of the iron group metals present on the catalyst. As
promoters for the catalysts according to the invention a large
15 number of elements are suitable. The following may be mentioned as
examples: alkali metals, alkaline earth metals, metals of group
VIB (W, Mo, Cr), Ti, Zr, Al, Si, As, V, Mn, Cu, Ag, Zn, Cd, Bi,
Pb, Sn, Ce, Th and U. One or more of these promoters are prefer-
ably introduced into the carrier by ion-exchange. Very suitable
20 promoter combinations for the iron catalyst component used accor-
ding to the invention consist of an alkali metal such as K, a
readily reducible metal such as Cu or Ag and optionally a metal
difficult to reduce, such as Al or Zn. An example of a very
suitable iron catalyst co~ponent to be used according to the
25 invention is a catalyst component containing iron, potassium and
copper in the crystalline silicate zeolite as carrier. If in the
process according to the invention use is made of an iron catalyst
component containing K as selectivity promoter, a catalyst con-
taining not more than 0.15 g of K per g of Fe is preferred, since
30 it has been found that if higher K concentrations are applied the
selectivity does not rise further while the stability substan-
tially decreases as a result of carbon deposition on the catalyst.
Very suitable promoter combinations for cobalt catalyst components
to be used according to the invention consist of an alkaline earth
35 metal and Th, U or Ce.
1~98~5~
-- 7 --
An example of a very suitable cobalt catalyst component to be used
according to the invention is a catalyst containing cobalt, mag-
nesium and thorium in the crystalline silicate zeolite as carrier.
Other very suitable cobalt catalyst components to be used accor-
ding to the invention are catalysts containing Co/Cr, Co/Zr, Co/Znor Co/Mg in the crystalline silicate zeolite as carrier. Very
suitable promoters for nickel catalyst components to be used
according to the invention are Al, Mn, Th, W and U.
If in the process according to the invention it is intended
to use a catalyst combination of which the catalyst component
having Fischer-Tropsch activity is iron, an iron catalyst compo-
nent is preferably chosen containing a promoter combination
consisting of an alkali metal, a readily reducible metal such as
copper or silver and optionally a metal difficult to reduce, such
as aluminium or zinc. A very suitable iron catalyst component for
the present purpose is a catalyst prepared by ion-exchange con-
taining iron, potassium and copper into the crystalline silicate
zeolite as carrier. If in the catalyst combination iron is used as
catalyst component having the required Fischer-Tropsch activity,
the process according to the invention is preferably carried out
at a temperature of 250-325C and a pressure of 20-100 bar.
If in the process according to the invention it is intended
to use a catalyst combination of which the catalyst component
having the required Fischer-Tropsch activity is cobalt, a cobalt
catalyst component is preferred containing a promoter combination
consisting of an alkaline earth metal and chromium, thorium,
uranium or cerium.
A very suitable cobalt catalyst for the present purpose is a
catalyst prepared by ion-exchange and containing cobalt, magnesium
and thorium in the crystalline silicate zeolite as carrier. Other
very suitable cobalt catalysts prepared by ion-exchange are
catalysts containing, in addition to cobalt, one of the elements
chromium, titanium, zirconium and zinc in the crystalline silicate
zeolite as carrier.
~98~
-- 8 --
If in the catalyst combination cobalt is used as catalyst
having the required Fischer-Tropsch activity, the process accor-
ding to the invention is preferably carried out at a temperature
of 220-300C and a pressure of 10-100 bar.
Very suitable catalysts for the process according to the
invention are
a) catalysts containing 0.05-10 parts by weight of iron and
0.025-5 parts by weight of magnesium per 100 parts by weight of
crystalline silicate zeolite carrier and prepared by ion-exchange
of the carrier with one or more solutions of salts of iron and of
magnesium followed by washing and drying the composition, calci-
ning it at a temperature of 300-600C and reducing it. Special
preference is given to such catalysts containing, in addition to
0.1-5 parts by weight of iron and 0.05-2.5 parts by weight of
magnesium, 0.05-2.5 parts by weight of copper as reduction promo-
ter and 0.1-1.5 parts by weight of potassium as selectivity pro-
moter per 100 parts by weight of carrier and calcined at 400-500C
and reduced at 250-450C.
b) catalysts containing 0.05-10 parts by weight of cobalt and
0.01-2.5 parts by weight of chromium per 100 parts by weight of
crystalline silicate zeolite carrier and prepared by ion-exchange
of the carrier with one or more solutions of salts of cobalt and
of chromium followed by washing and drying the composition,
calcining it and reducing it at a temperature of 300-750C.
~articular preference is given to such catalyst containing, in
addition to 0.1-5 parts by weight of cobalt and 0.05-1 parts by
weight of chromium, calcined at 300-700C and reduced at 300-700C;
c) catalysts containing 0.05-10 parts by weight of cobalt and
0.01-2.5 parts by weight of zirconium, titanium or chromium per
100 parts by weight of crystalline silicate zeolite carrier and
prepared by ion-exchange of a silicate carrier with one or more
solutions of salts of cobalt and zirconium, titanium or chromium,
followed by washing and drying the composition, calcining at
350-700C and reducing it at 200-700C.
~198451
In the process according to the invention catalysts are used
that are prepared by ion-exchange of the carrier, preferably with
one or more aqueous solutions of salts of ruthenium or of metals
of the iron group and salts of promoters, followed by washing with
5 washing water, drying and calc~ning the composition.
The ion-exchange ability of crystalline metal silicates is
well known. In crystalline metal silicates, the electrovalence of
the metal in the structure is balanced by the inclusion of a
cation in the crystal. The cation is most commonly an alkali
metal, such as sodium or potassium. The cations of either the
synthetic or naturally occuring aluminosilicates can be exchanged
for the mono- or polyvalent cations which are of a suitable
physical size and configuration to diffuse into the intracrystal-
line passages in the silicate structure~ The original cation can
be replaced by another cation e.g. by a hydrogen ion or by an
am~onium ion. In general, any suitable acid or salt solution such
as a sulphate or nitrate can be used as a source of cations to be
exchanged into the silicate.
The theoretical exchange capacity of the crystalline silicate
is represented by the number of equivalents of cations, e.g.
sodium ions,,which balance the electroneutrality of the crystal-
line silicate. The exchange capacity varies according to the
particular type of sieve involved. In practice, not all of the
cations in the silicate are readily replaced with the desired
cations, so that the effective exchange capacity is often somewhat
less than the theoretical exchange capacity. The extent of the
exchange depends on such factors as the type of sieve, cations in
the sieve, cations to be exchanged, type of solvent (water,
alcohol) and temperature of exchange. Clearly, there is a limit to
the amount of catalytically active metal which can be ion-exchanged
into the crystalline silicate.
The ion-exchange is preferably carried out at a temperature
in the range from 20 to 200C.
Following the ion-exchange step, the ion-exchange solution is
removed from the zeolite con~aining the catalytically active metal
45~
-- 10 --
exchanged therein, for example by filtration. The zeolite is then
washed preferably with the ion-exchange solvent to remove any
unreacted metal and the wash liquid is removed, for example by
filtration. The zeolite cake from which the wash liquid has been
removed usually contains about 50% solids. Either with or without
further adjustment of the solvent content, the zeolite can be
shaped to desired size. If desired one or more binders and/or
extrusion aids can be added. The zeolite may then be dried, and
the shaped catalyst is calcined, at a temperature of from about
10 300 to about 600C, to form the ~inished catalyst.
In the preparation of the catalysts the metals can be deposi-
ted on the carrier in one or more steps. Between the separate
ion-exchange steps the material may be dried. For the preparation
of catalysts with a high metal content the use of a multi-step
15 technique may be necessary. The salts of the iron group metals and
the salts of the promoters can be deposited on the carrier separate-
ly from different solutions or together from one solution.
In the process according to the invention the intention is to
convert the largest possible quartity of the C0 prese~t in the
20 feed into hydrocarbons over a catalyst containing one or more
metal components with catalytic activity for the conversion of an
H2/C0 mixture into hydrocarbons, which metal components are chosen
from the group formed by iron, cobalt, nickel and ruthenium. To
this end the H2/C0 molar ratio in the feed is suitably at least
25 1.0 and preferably 1.25-2.25.
The process according to the invention can very suitably be
carried out by conducting the feed in upward or downward direction
through a vertically mounted reactor containing a fixed bed of the
catalyst or by passing the gaseous feeds upwardly through a fluid
30 catalyst bed. The process can also be carried out using a suspen-
sion of the catalyst or catalyst combination in a hydrocarbon oil.
The process is preferably carried out under the following condi-
tions: a temperature of 125-350C and in particular of 175-275C
34~
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 Examples.
Example 1
The crystalline aluminosilicate ZSM-5 was prepared according
to the recipe as described in U.S. patent specification No.
3,702,886. The silicate obtained was first transférred into the
ammonium form by ion-exchange with a 2Normal NH4N03 solution. The
ammonium form of the ZSM-5 was ion exchanged with an aqueous
solution of RuC13 (5% wt.) during 48 hours. The catalyst was then
washed with water, dried and subjected to a 2-hour calcination at
500C with air at atmospheric pressure and reduced for two hours
at 280C with H2 at 4 bars. The resulting catalyst had the follo-
wing composition:
1.7 Ru/66 SiO2/1 A12O3 (parts by weight). A gas mix~ure consisting
of H2 and C0 (H2/CO = 1) was passed over this catalyst applying
the following conditions:
gas hourly space velocity: 1000 1 (NTP)/lh
pressure: 20 bar
20 temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 20.0% wt. The
space-time yield was 67 grams of hydrocarbons per litre of cata-
lyst volume per hour.
The selectivity is given in the following table:
C 1 + C2 4% wt.
C 3 + C4 : 16% wt.
C 5 - C12: 78% wt.
C13 - C19: 1.5% wt.
C20 + : 0.5% wt. From this table it can be seen that the
30 yield of desired hydrocarbons boiling in the gasoline boiling
range (C5-C12) is very high compared with those boiling below and
above the preferred range.
The condensed liquid phase contained 40% wt aromatics, only
trace amounts of durene being present.
S~
Comparative experiment 1
The ZSM-5 was prepared as shown in Example 1. It was impreg-
nated with an aqueous solution of ruthenium chloride, dried,
calcined during 2 hours at 500C in air and reduced for 2 hours at
280C with hydrogen at 4 bar pressure in order to obtain a cata-
lyst having the composition: 1.7 Ru/66 SiO2/1 A1203 (parts by
weight). Using this catalyst under the conditions described in
Example 1 hydrocarbons were formed from a H2/C0 gas mixture (H2/C0
= 1). The conversion was 13% wt. The space-time yield was 26 grams
10 of hydrocarbons per litre of catalyst per hour.
The selectivity was:
C1 + C2 : 25% wt.
C3 + C4 : 40% wt.
C5 - C12: 35% wt.
15 C13 _ C19: 0% wt.
C20 + : 0% wt.
An inferior result as regards the yield of gasoline components
(C5-C12) was thus obtained. Moreover no aromatics were present in
the product.
20 Example 2
Crystalline silica was prepared according to the recipe of
silicalite disclosed in column 6 of U.S. patent specification
4,061,724.
The crystalline silica obtained was first transferred to
25 ammonium form by ion-exchange with a 2N NH4 N03 solution. The
a~monium form was ion-exchanged with an aqueous solution of Co
(NH3)6(N03)2 (15% wt) during 24 hours.
The catalyst was then washed with water, dried, calcined two
hours a~ 500C and subjected to a 24 hours' reduction with hydro-
30 gen at 575C and 1 bar abs.
This catalyst had the following composition: 100 SiO2.2.5 Co
(parts by weight).
A H2/C0 mixture (H2/C0 = 1) was passed over this catalyst
applying the following conditions.
gas hourly space velocity: 1000 1 (NTP/1 h)
45~
- 13 -
pressure: 20 bar
temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 51% ~t. The
space-time yield was 112 grams of hydrocarbons per litre of
catalyst per hour.
The selectivity is given in the following table:
Cl + C2 16%
C3 + C4 15%
C5 C12: 58%
C 3 - Clg: 8%
C20 + : 3%
