Note: Descriptions are shown in the official language in which they were submitted.
~ 7 ~4~
The invention relates to a process for the
manufacture of mixtures of oxygen-containing C2 compounds
and low-molecular olefins. It relates in particular
to the manufacture of mixtures of acetie acid, aeetal-
dehyde, ethanol, ethylene and propylene by reactingearbon monoxide with hydrogen in the gas phase.
Theré are already numerous processes known in
whieh the gas phase reaction of synthesis gas, that is to
say of mixtures of earbon monoxide and hydrogen, on
eatalysts containing iron or eobalt, to give mixtures of
oxygen-eontaining carbon eompounds and saturated or
unsaturated hydroearbons is deseribed This reaetion
of synthesis gas, generally known as ~he Fiseher-Tropsch
proeess, is not very seleetive, however, and leads to
mixtures having a broad and not very speeifie distribution
of products in whieh the individual components ean eontain
up to 20 or more earbon atoms. Although the addition of
.-alkali,espeeially potassium earbonate or potassium oxide,
produees a redueed formation of m~ane and an increased
formation of olefins in the case of these eatalysts, it
r~sults, on the other hand, in an increased growth of
ehains, that is to say the formation of higher-molecular
eompounds is promoted by the addition of alkaii (eompare
B~ssemeier ~t al., Hydrocarbon Processing, Nov. 1976,
page 161).
It is also known from German Offenlegungssehrift
2,507,6~7 that olefins containing two to four earbon atoms
in the molecule c~n be formed preferentially, together
with oxy~en-containing compovnds, on catalysts containing
7~ 49
3 --
mainly mang~n~se . However, in this process a large
part of the carbon monoxide is converted into carbon
dioxide; in addition the proportion of oxygen-containing
compounds in the reaction mixture is very low.
Recently, numerous processes have also been dis-
closed which have as their subject the gas phase reaction
o~ synthesis gas on catalysts containing rhodium and
which lead, in a high degree of selectivity, to oxygen-
containing compounds which preferably have two carbon
atoms in the molecule. Such processes have been dis-
closed, for example, in German Auslegeschrift 2,503,233,
German Auslegeschrift 2,503,204, German Offenlegungsschrift
2,628,463 and U.S. Patent Specification 4,096,164 or have
been suggested in German Patent Applications
P 2,814,3~5,9, P 2,814,427.6, P 2,825,495.7, P 2,825,59~.3,
P 2,850,110.2 and P 2,850,201. 4.
Besides oxygen-containing products having pre-
ferably two carbon atoms in the molecule, these processes
based on rhodium as the catalytically active component
also produce in the main carbon dioxide, methane and only
small quantities of other saturated or unsaturated hydro-
carbons. Thus, for example, according to M.M. Bhasin
et al. (J. of Catalysis 54, 120 (1978)), in the reaction
of synthesis gas at 300C and 70 bars on a catalyst con-
taining 2.5% by weight of rhodium, only 3.4% of the carbonmonoxide converted react to give saturated and unsaturated
hydrocarbons having two or more carbon atoms, while 43.1%
of the carbon monoxide react to give o~ygen-containing
C2 compounds and 52% react to give methane.
.
~47~49
-- 4 --
By usi-ng catalysts which contain, besides rhodium,
also promoters, such as magnesium or manganese, it is
possible to obtain the oxygen-containing compounds, such
as acetic acid, acetaldehyde and ethanol, in an improved
degree of selectivity, Even if the most selective
production possible of these oxygen-containing compounds
is o~ primary importance in many cases, the simultaneous
producti.on of low-molecular olefins, which are indus-
trially important primary products of the chemical
industry, can, however, be important, particularly if an
increas~ forrnation of olefins is associated with the
reduced conversion into methane as a by-product.
It has now been found that mixtures of oxygen-
containing C2 compounds and a hi~h proportion of low-
molecular olefins are obtained if catalysts are usedwhich, besides rhodium and optionally promoters, also
contain 0.1 to 5.0% by weight of alkali metals in the
form of oxides, hydroxides, salts or complex compounds.
It has been found in addition that the addition of the
alkali metal compounds increases the activity of the cata-
lys~s and reduces the selective forrnation of methane.
The invention relates, therefore, to a process
for the manufacture of mixtures of acetic acid, acetalde-
hyde, ethanol and olefins ha~ing two to four carbon atoms,
in a 1:1 to 2.5:1 molar rat.io of the said oxygen-containing
compounds to the olefins, by reacting carbon monoxide ~nd
hydrogen in the presence of catalysts containing rhod..um
and op-cionally promoters, in the ~as phase at ternperatures
between 150 and 350C and pressures between 1 and 300 bars,
~ .
1147, 49
wherein the catalysts contain 0.1 to 5.0% by weight of
alkali metal in the form of oxides, hydroxides, salts
or complex compounds.
The result found, that alkali metal ions in low
concentrations promote the formation of olefins, reduce
~he conversion of the synthesis gas into methane and
additionally increase the total activity of the catalysts,
was surprising and could not have been foreseen.
In the process according to the invention, the
olefins formed are chiefly ethylene and propylene, as well
as small quantities of butenes, and the oxygen-containing
compounds formed are acetic acid, acetaldehyde and
ethanol and also such products as can be for~ed under the
reaction conditions in a secondary reaction, for example
by esterification or condensation, above all ethyl
acetate and the diethylacetal of acetaldehyde.
The overall selectivity for the formation of
oxygen-containing products and olefins is generally between
70 and 90%, relative to carbon monoxide converted. The
remainder of the carbon monoxide is converted into alkanes,
includinO methane,in~ carbon dioxide and, in small
quantities, into oxygen-containing compounds having three
or more carbon atoms.
The molar ratio of o~ygen-containing C2 compounds
to olefins is between 1:1 and 2.5:1, molar ratio being
understood to mean the ratio of the molar sum of the
oxygen-containing C2 compounds, that is to say acetic
acid, acetaldehyde and ethanol, to the molar sum of the
olefins ha~ing 2 to 4 C atoms.
'7'7
-- 6 --
Catalysts containing rhodium and optionally
promoters and also 0.1 to 5.0,h by weight of alkali cn a
support are used for the reaction, according to the
invention, of the synthesis gas.
The supports used can be commercially available
support materials having a varying specific surface area.
However, supports having a specificsurfacearea of50 to
1,000 m2/g are preferred. Suitable examples are
silica, natural or synthetic silicates of elements of the
second to eighth group of the periodic system (that is to
say, for example, the silicates of magnesium, calcium,
aluminum, the rare earths, titanium, zirconium or man-
ganese), and also aluminum oxide, titanium dioxide,
zirconium dioxide, thorium dioxide, zeolites and spinels.
Rhodium can be present on the carrier in the
metallic form or in a valency state less than three, that
is to say as a co~plex compound of zero-valent rhodium or
as a salt or complex compound of monovalent or divalent
rhodium. It is possible to use salts or comp]ex com-
pounds of rhodium of any desired valency state as the
starting material and, if appropriate, subseauently to
c~rry out a reduction stage, such as is described later
in the text. Examples of suitable compounds of rhodium
are the chlorides, bromides, iodides, nitrates or car-
boxylates or double salts of rhodium with alkali metalhalides, such as, for example, dipotassium trichloro-
rhodate. Complex compounds which, as well as rhodium
and halogen, also contain complex-forming ligands, such
as trialkylphosphine, triarylphosphine, ethylenediamine,
11~7749
7 --
pyridine, carboll mGnoxide, oleflns or water, are also
suitable, that is to say, for example, tris-triphenyl-
phosphine-rhodium-I chlorid~ bromide or iodide, tris-
triphenylphosphine-rhodium-III chloride, dichloro-bis-
ethylenediamine-rhodium-I chloride, tris-ethylenediamine-
rhodium-III chloride, bis-tri-o-tolyl-phosphine-rhodium-
II chloride, carbonyl-bis-triphenyl-phosphine-rhodium-I
bromide or dicesium carbonyl-pentachlororhodate-III.
In addition, compounds of rhodium,in which it is linked
ionically or as a complex to a support,are also suitable.
Examples of these are the zeolites and ion exchangers which
have been subjected to an exchange reaction with rhodium
halides.
The alkali metal compounds used are the oxides,
salts or complex compounds of lithium, sodium, potassium,
I~bidium or cesium or mixtures thereof, that is to say,
for example, the oxides, hydroxides, carbonates, chlorides,
bromides, iodides, nitrates, acetates, silicates and/or
aluminates of the alkali metals. The sodium compounds
~0 are par~icularly preferred.
Besides rhodium and alkali metal compounds, the
catalysts also preferably contain promoters or activators.-
The comblnation magnesium/halide ions and also manganese
are particularly suitable as promoters or activators.
If appropriate, however, the catalysts can also contain
substances which affect the selectivity of formation of
the individual oxygen-containing products, such as iron,
zirconium, nafnium, lanthanwm, platinum, mercury, molybdenum
and tungsten. The said elements, which are effective as
~i4L'~749
-- 8 --
promoters or a~fect the selectivity, can be in the form
of simple inorganic or organic compounds, such as, for
example, chlorides, bromides, nitrates, carbonates,
oxides, hydroxides, silicates or acetates. Complex
compounds of these elements containing inorganic or
organic ligands, such as, for example, potassium magnesium
trichloride, trisodium hexacyanomanganate-III or di-
potassium hexacyanoferrate-II, and also chloro-complex
compounds of -the said elements with rhodium of the general
formula Mem[RhC16]n wherein Me represents one of the said
metals, for example Mg3[RhC16]2,are also suitable.
The halide ions used in combination with ~agnesium can be
the chlorides, bromides or iodides. The halide can be
applied in the form of a rhodium, alkali metal or magnesium
compound; suitable compounds have already been mentioned.
It is also possible, however, to employ halogen-
~ree magnesium compou~ds, for example the acetates or
nitrates, and to apply the halide ions to the support by
subsequent treatment with hydrogen halide or impregnation
with a metal halide. It is also possible to use an
organic compound containing halogen (such as, for example,
l,l-dichloroethane) from which the halogen can be libera~ed,
in order to adjust the halogen content of the catalyst,
after the i~pregnation with the magnesium compound, to the
figure necessary for the selective conversion of synthesis
gas.
Examples of suitable solvents for the active com-
ponents are water and anhydrous or aqueous carboxylic
acids, in particular ~a-ter and acetic acid.
.. . .
1~7~ 9
_ g _
In order to build up the catalyst, the support is
impregnated, simultaneously or in successive stages in
`any desired sequence, with the rhodium compound, the
alkali metal compound and, if appropriate, the promoters
or the addltives which influence the selectivity.
A particularly preferred form of preparing the
catalyst consists in impregnating the support with the
solution of the alkali metal compound and of the promoter,
drying the mixture, then sintering it at temperatures
between 400 and 1,200C and thereafter applying the
rhodium compound.
The alkali metal and the promoters can, however,
also be incorporated in a substance possessing a lattice
structure, for example in a carrier substance containing
silicate or aluminum oxide, such as silica, alumir.um oxide
or aluminum silicate. A further ad~antageous possible
means consists in binding the alkali metal or the promoters
by means of ion exchange to cation exchangers which are
also suitable as carriers for the rhodiurn and are stable
under the experimental conditions, for example the natural
or synthetic aluminum silicates which are known as
molecular sieves.
Before the catalyst is used for the con~ersion of
synthesis gas, it must also be reduced, if the reaction
is to take place on metallic rhodiu~ or if trivalent
rhodium has been used for the preparation of the catalyst.
The reduction can be carried out in the reactor itself or
in a separate apparatus. Examples of suitable
reducing agents are hydrogen, carbon monoxide, methanol
-- 10 --
or acetone. ~eduction temperatures above 300,
preferably between 35~ and 550C, produce metallic
rhodium; reduction temperatures below 300C, preferably
between 100 and 275C, produce a lower (non-metallic)
valency state of the rhodium.
Frequently it is expedient not to carry out the
reduction using the undiluted reducing agent, but to
dilute the ]atter ~lith an additional proportion of inert
gas, such as, for example, nitrogen or carbon dioxide.
The concentration of rhodiurn, the alkali metals
and, if appropriate, the promoters can vary within wide
limits. In general, the values, expressed in terrns of
the metals, are between 0.1 and 15% by weight for rhodium,
between 0.1 and 5.0% by weight for the alkali metals and
between 0.1 and 20% by weight ~or the promoters. If
the combination magnesiumjhalide ions is employed, 0.1 -
10% by weight of magnesium and 0.1 - 10% by weight o~
halide ions are used. The alkali metal conccntration
affects the selectivity of forrnation o~ the olefins and,
specifically, the selectivity of forrnation of the olefins
increases as the concentration increases.
The process according to the invention is carried
out by passing gas mixtures which consist entirely or
predominantly of carbon monoxide and hydrogen and, in addi-
2~ tion,in somecases can alsocontain other cornponents, such asnitrcgen, argon, carbon dioxide or methane, over the cata-
lyst. In -this process the molar ratio of carbon mon-
oxide to hydro~en can vary wi-thin wide limits. Molar
ratios bet~een 5:1 and 1:5, and particularly between ~:1
749
-- 11 --
and 1:3, are preferred. The reaction -temperatures are,
in general, bet~leen 175 and 375C, preferably bet~een
200 and 350C, and the reaction pressures are between 1
and 300 bars, preferably between 10 and 200 bars.
It is expedient to adjust the temperature and
pressure to one another in such a way that a high degree
of selectivity for the formation of the oxygen-containing
compounds is ensured and the exothermic formation of
methane, ~hich is favored at higher temperatures, remains
slight. High pressures,and temperatures as low as
possible will therefore be preferred. The con~ersion
of carbon monoxide should generally not exceed 50/0 in this
process, since higher conversions can readily lead to an
increased formation of by-products, it bein~ also possible
for higher-molecular, liquid hydrocarbons and oxygen-
containing products to be formed in addition to methane
and carbon dioxide.
- The conventional fixed bed rcactors can be used for
carrying out the process, and it can be advantageous for
improved removal of heat to keep the thickness of the layer
of catalyst low. Furthermore, reactors with a moving
catalyst bed or fluidized bed reactors are also suitable.
A particularly preferred embodiment of the inven-
tion &onsists in carrying out the reaction in a circulating
gas apparatus in which the unreacted gas mixture is re-
cycled into the reactor after removing the condensible
reaction products.
This procedure is particularly economical and, by
diluting the fresh gas with the residual gas o~ lower
'749
- 12 -
hydrogen content ~lich is fed back as recycle
gas, makes possible higher reaction temperatures and
thus higher space/time yields at unàltered selectivities.
Recycle gas equipment with an internal or external cir-
culation of gas is suitable for this procedure.
The essence of the invention will be illus-
trated in the examples which follow, these examples being
in~ended in no way to be limiting,
Experimental Series A
(The use,of commercially availabl'e supports containing a
varying amount of sodium, already present).
Portions of 52 g (120 ml) of the silica supports
listed in Table 1 are impregnated at room temperature
with a solution of 1,08 g of magnesium chloride hexa-
,hydrate in 66 g of ~ater and are then dried for 2 hoursat 80C and for 2 hours at 150C. The supports are
then sintered for 30 minutes at 800C. The sintered
support is then impregnated at room temperature with a
solution of 4.0 g of rhodium-III chloride . x H20 (37.4
by weight of Rh) in 66 g of water and dried in a manner
simil~r to that described above. The catalysts are
then reduced in a glass vessel by passing 30 l(STP)/hour
of hydrogen over them for 3 hours at 225-275C under
normal pre~ssure. They contain 2.7% by weight of Rh
and 0.24% by weight of Mg.
' 100 ml of the catalyst are put into a stainless
.steel reaction tube 810 mm long with an internal diameter
o~ 16 mm, which is equipped with a coaxia7 thermoMeter
shaathwith an external diameter of 6 ~m. The reactor
'74
-- 13 --
temperature is adjusted by means of a salt bath.
70 l(STP)/hour of a mixture of carbon monoxide
and hydrogen in a 1:1 volume ratio is passed over the
catalyst at 20 bars and an internal temperature of 275C.
The reaction mixture is cooled and the incondensible
components are allowed to expand. The gaseous com-
ponents and the condensed reaction products are determined
by gas chromatography. The results listed in Table 1
are obtained.
.
-- 14 _
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'749
Experiment-~l Ser.es B
__
(The use of suppor~s which have been doped with various
alkali metal salts).
The quantities of alkali metal salt indicated in
Table 2, ~hich correspond in each case to 8.16 mmoles of
the anhydrous compound, are each dissolved in 66 g of
ater. These solutions are used to impregnate in each
case 52 g (120 ml) of the silica support mentioned in
Comparison Example 1 of Experimental Series A. After
being impregnated, the support is dried for 2 hours at
80C and for 2 hours at 150C and is finally sintered for
30 minutes at 800C. Each of the supports is then
impregnated with a solution of 1.08 g of magnesium
chloride hexahydrate in 66 g of water and is dried and
sintered in the same manner as described above. The
supports pre-treated in this way are then additionally
impregnated with a solution of 4.0 g of rhodium-III
chloride.x H20 (37.4% by weight of Rh) in 66 g of water
and are dried for 2 hours at ~0C and for 2 hours at
150C and are finally reduced in a glass vessel by
passing 30 l(STP)/hour of hydrogen over them for 3 hours
at 225-275C under normal pressure. The catalysts
contain 2,7% by weight of Rh and 0.24% by weight of Mg.
These catalysts are tested in the reactor des-
cribed in Experimental Series A under the reaction con-
ditions indicated in that seri es . The results are
listed in Table 2.
~7749
-- 16 --
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'74~1
-- 17 --
~eriment;a3 .~erles C
(Recycle gas apparatus)
The apparatus consists of a heatcd reaction tube
with a length of 1 m and an internal diameter of 24.4 mm,
made of corrosion-resistant steel and having a coaxial
thermometer sh~a ~ ~t,h an external diameter of 12 ~m, a
condenser placed do~mstream, a receiver for the condensate
and a compressor for recycling part of the non-condensed
gases to the reactor (recycle gas), In each case 250 ml
of the catalysts described below are charged. After
flushing the apparatus with nitrogen, a pressure of
100 bars is initially set up by means of-a synthesis gas
ccmposed of 49% by volume of C0, 49% by volume of H2, 1%
by volume of C02 and 1% by volume of N2 (and small
quantities of other components) and the reactor is heated
to 275C, During the heating-up period and in the
further course of the experiments, 1,000 l(STP)/hour of
synthesis ~as of the above composition are fed via the
suction side of the compressor to the recycle gas and,
together with ~he latter, are pass~d over the catalyst,
The gas circulation rate is about 5,000 l/hour, The gas
mixture leaving the reactor is cooled to about +5C in a
brine-cooled condenser and the condensed constituents are
collected in the receiver, The non-condensed residual
?5 gas is mixed with fresh synthesis gas and recycled to the
reactor via the compressor. Part of the residual gas
is bled off through a constant-pressure valve in order to
maintain the pressure aIld to remove the olefins and by
products. Compariscn Example 3 and EY.amples 11-13
,
- 18 -
~ are carri~d cut by this method. The results are
listed in Table 3. The catalyst employed for
Comparison Examp]e 3 is 250 ml of the catàlyst mentioned
in Comparison Example 1. 250 ml of the catalyst
mentioned in Example 4 are used for ~xarnple 11 and
250 ml of the catalyst mentioned in Example 5 are used
for Example 12. For Example 13, 250 ml of a catalyst
prepared as follows are employed:
120 g of the silica support mentioned in
Comparison Example ~, containing 0.04% by weight of Na,
are impregnated with a solution of 2.49 g of magnesium
chloride hexahydrate and 1. 55 g of sodi~m acetate in
152 g O~ ~later and are dried for 2 hours at 80C, 2 hours
at 120C and 2 hours at 150C. The support is then
impregnated with a solution of 9.24 g of rhodium-III
chloride (37.4% by weight of Rh) in 152 g of water and
is again dried in the same manner as described above.
The catalyst is then reduced in a glass vessel by passing
50 l(STP)/hour of hydrogen over it for 3 hours at
225-275C under normal pressure. The finishcd catalyst
contains 2.7% by weight of Rh, 0.240/o by weight of Mg,
0.37% by weight of Na and 1.9~ by weight of C1.
1~7749
-- 19 -- ..
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