Note: Descriptions are shown in the official language in which they were submitted.
11~703~ 12,310
BACKGROUND OF THE INVENTION
This invention pertains to the carbonylationof aliphatic alcohols and in particular to promoted
manganese catalysts therefor.
A variety of transition metal complexes are
known to catalyze halide promoted carbonylation of
methanol to acetic acid. These systems require severe
reaction conditions and/or the use of expensive metal
catalysts in order ~o provide commercially
economical processes. For example, a process is des-
cribed in U.S. 4,102,920 for the carbonylation of alcohols
among other substrates in the presence of a catalyst
system comprising a Group VIII metal component and a
halogen component with a polydentate chelating phos-
phorus or arsenic ligand.
It is an ob;ect of this invention to provide an
inexpensive catalyst system which permits the carbony-
lation of saturated aliphatic alcohols at low tempera-
tures, that is, below about 200C. in order to minimize
corrosion.
It is a further object of this invention to
provide an inexpensive catalyst system for the carbony-
lation of saturated aliphatic alcohols which can be
operated at low pressures, that is, below about 2000
psia in order to min~ize equipment cost.
It is another object of this invention to
provide a catalyst system which provides primarily
aliphatic acids from the corresponding alcohols, but
which also provides esters or anhydrides by controlling
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reaction conditions.
These snd other objects will become apparent
to those skilled in the art upon a further reading of the
specification.
SUMMARY OF THE INVENTION
A catalyst system for the carbonylation of
saturated aliphatic alcohols has been found meeting the
above objects which comprises a compound of manganesei
which is soluble in the reaction mixture and a promoter
selected from the group consisting of iodine and an
alkyl iodide wherein the alkyl moieties of the iodide
contain 1 to about 6 carbon atoms. This catalyst can be
used withbest results at a temperature ~rom about 100C.
to about 180Co in a conventional carbonylation process
wherein a saturated aliphatic alcohol having the formula
ROH, where R is alkyl having values of 1 to about 18,
is contacted with carbon monoxide or a mixture of carbon
monoxide and hydrogen at supra atmospheric pressures
below about 2000 psi.
A preferred pressure range is about 500 psi
to about 2000 pæi.
A preferred temperature range is about 120C.
to about 150C.
DESCRIPTION OF THE INVENTION
A general procedure for utilizing the carbony-
lation çatalyst of this invention is described below.
A 500 cc high-pressure reactor equipped with
a glass liner is charged with a solution composed of a
catalytic amount of manganese compound dissolved in a
known amount acetic acid and/or methanol together with
r 3 ~
~S7~38
12,310
a controlled amount of a halide promoter and optionally
an inert diluent for use in subsequent analytical work as
an internal standard. The system is purged and then
placed under a prescribed pressure of carbon monoxide
or a mixture of carbon monoxide and hydrogen, heated
to the desired temperature and agitated by means of
rocking. Upon completion of each experiment which may
vary in time from about 15 minutes to about 12 hours,
the system is cooled, vented, and the contents of the
reactor isolated for spectral infrared or nuclear
magnetic resonance analysis as well as for vapor phase
chromatographic analysis.
The actual form of the manganese catalyst pre-
cursor used in this invention is not critical since man-
ganese in a variety of oxidation states provides the re-
quired catalytic activity. Thus, for example, one may use
manganese in the -1 valence state as, for example, in
NaMn(C0)5, manganese in the zero valence state as found
in compounds, such as, Mn2C010, manganese in the +1
valence state as found in compounds, such as, IMn(C0)5,
or manganese in the +2 valence state as found in such
compounds as Mn(OAc)2 . 4 ~ 0. These systems are
extremely complicated and abstruse because of the various
complexes which can form in reaction media. This is
reflected in the speed with which reaction is initiated
which appears to lie between the extremes of immediate
gas uptake indicating immediate activity of the catalyst
as soon as the proper reaction conditions of temperature
and pressure have been reached and evidence of a delayed
4.
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~L~57~38
activity indicating an induction period in order to
allow formation of certain reactive species or complexes.
While the ratio of manganese to promoter is
not narrowly critical, a ratio of promoter:manganese
catalyst of about 5 to about 7 is preferred.
The carbonylation react~on using this ca~alyst
system can be practised either as a batch process or a
continuous process.
While commercial interest center mainly in
the use of this catalyst system for the carbonylation of
methanol, it is equally applicable to higher alcohols
ranging from ethanol to octadecanol
Furthermore, by appropriate control of the
composition of the reaction solvent, that is, by con-
trolling the amount of water, methanol, acetic acid~
acetone, etc., one may selectively favor the formation
from methanol in this carbonylation reaction of acetic
acid, methyl acetate or acetic anhydride permitting the
scope of the reaction to produce a variety of industrially
important chemicals.
The form in which the iodine promoter i9 added
to the mRnganese catalyst is not critical. Thus, for
example, one may use elemental iodine, hydriodic acid,
alkyl iodides wherein the alkyl group contains 1 to abo~t
6 carbon atoms as for example, methyl iodide, ethyl
iodide, propyl iodide, butyl iodide, pentyl iodide,
hexyl iodide, and the likeO
The in~ention is further described in the
examples which follow. All parts and percentages are
by weight unless otherwise specified.
5.
~ 310
, . ~
7 ~ 3
Example 1
A 500 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
Mn2(CO)10 1.6 g, CH3I 1.0 g, and C6H5CH3 1.0 g. The
system was then purged with ca. 1000 psi of carbon
monoxide ~nd then charged with 1500 psi of carbon monoxide.
The reactor was heated to 120C. at which time the solu-
tion was agitated by mesns of rocking. Upon completion
of the experiment, 5.5 hours, the rocking was stopped,
the system cooled to 20-25C., the remaining gas was
vented, and the liqu~d contents isolated for analysis.
Vapor phase chromatographic data was obtained on an
HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed w~th 10% SP-1200/1% H3P04
(low polarlty ester sold by Supelco Co. used as the
stationary phase and contain~ng 1% H3P04) on 80tlOO
Chromo~or ~ W/AW (acid washed firebrick support sold ~y
Johns Manv~lle).
Analy~is of the final reaction solution showed
lt to contain CH30H 27.5 g ~0.86 mol) and CH3C02CH3
6.6 g (0.09 mol).
Example 2
A 500 cc high pressure reactor equipped with a
glass l~ner was charged with the following: CH30H 32 g,
(CO)lo 1.6 g, CH3I 1.0 g, 47% aq. HI 0.25 g and
C6H5CH3 1.0 g. The syst~m was then purget with ca. 1000
p5i of carbon monoxide and then charged with 1500 psi of
carbon monoxide. The reactor was heated to 120C. at
which time the solution was agi~a~ed by means of roc~ing.
6.
~ j
12,310
~57~38
Upon completion of the experiment, 5.7 hours, the rocking
was stopped, the system cooled to 20-25C, the remaining
gas was vented, and the liquid contents isolated for
analysis. ~apor phase chromatographic data was obtained
on an HP-5830 gas chromatograph equipped with 6 ft x l/8"
stainless steel column packed with 10% SP-1200/1% H3P04
on 80/lO0 Chromosorb W/AW.
Analysis of the final reactor solution showed
it to contain CH30H 23 . 7 g and CH3C02CH3 ll . l g.
Example 3
A 500 cc high pressure reactor equipped with
a glass liner was charged with the following: CH30H 32 g,
Mn2 (CO)lo 1.6 g~ 47% aq. HI 0.25 g, and C6H5CH3 1.0 g.
- The system was then purged with caO 1000 psi of carbon
monoxide and then charged with 1500 psi of carbon
monoxide. The reactor was heatet to 150C. at which
time the solution was agitated by means of rocking. Upon
completion of the experiment, 3.0 hours, the rocking was
stopped, the system cooled to 20-25C., the remaining
gas was vented, and the liquid contents isolated for
analysis. Vapor phase chromatographic data was obtained
on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1~00/1% H3P04
on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 31.0 g and CH3CO2CH3 l.0 g.
~1~L5703~ 12 9 310
Example 4
A ~00 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
Mn2 (C0)10 1.6 g, CH3I 0O5 g, 47% aq. HI 0.25 g, and
C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500
psi of carbon monoxide. The reactor was heated to 150C.
at which time the solution was agitated by means of rock-
ing. Upon completion of the experiment, 3.0 hours, the
10 rocking was stopped, the system cooled to 20-25C., the
remaining gas was vented, and the liquid contents isolated
for analysis. Vapor phase chromatographic data was ob-
tained on an HP-5830 gas chromatograph equipped with
6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final reaction solution was analyzed and
found to contain CH30H 29.6 g and CH3C02CH3 5.5 g.
Example 5
A 500 cc high pressure reactor equipped with a
20 glass liner was charged with the following: CH30H 32 g,
Mn2(C0)10 1.6 g, CH31 3.6 g, 47% aq. HI 0.25 g, and
C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi
carbon monoxide. The reactor was heated to 150C. at which
time the solution was agitated by means of rocking. Upon
completion of the experiment, 3.0 hours, the rocking was
stopped, the systesll cooled to 20-25C., the remaining gas
was vented, and the liquid contents isolated for analysis.
Vapor phase chromatographic data was obtained on an HP-5830
r 8 ~
12,310
~ 57 0 3~
gas chromatograph equipped with 6 ft x 1/8" stainless
steel column packed with 10~/o SP-1200/1% H3P04 on 80/100
Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 12.2 g and CH3C02CH3 24 g.
Exam~le 6
A 500 cc high press~re reactor equipped with a
glass liner was charged with the following: CH30H 48 g,
Mn2(CO)10 1.6 g, CH3I 5.4 g, 47/0 aq. HI 0.25 g, and
C6H5CH3 1.5 g. The system was then purged with ca. 1000
psi of carbon monoxide and then charged with 1500 psi
carbon monoxide. The reactor was heated to 150C. at
which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking
was stopped, the system cooled to 20-25C., the remaining
gas was vented, and the liquid contents isolated for
analysis. Vapor phase chromatographic data was obtainet
on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04
on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 20.3 g and CH3C02CH3 31 g.
Example 7
A 500 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
CH3C02H 39.6 g, Mn2(CO)10 1.0 g, CH3I 5-8 g, 47% aq-
HI 0.25 g, and C6H5CH3 3.0 g. The system was then
purged with ca. 1000 psi of carbon monoxide and then
~ 12,310
L57038
charged with 2000 psi carbon monoxide. The reactor was
heated to 155C. at which time the solution was agitated
by means of rocking. Upon completion of the experiment,
3.0 hours, the rocking was stopped, the system cooled to
20-25C., the remaining gas was vented, and the liquid
contents isolated for analysis. Vapor phase chromato-
graphic data was obtained on an HP-5830 gas chromatograph
equipped with 6 ft x 1/8" stainless steel column packed
with 10% SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH3OH 5.6 g, CH3C02CH3 47.3 g and CH3C02H
14.8 g.
Example 8
A 500 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 41.6 g,
Mn2(CO~10 0.9 g, CH3I 5.1 g, 47% aq. HI 0.1 g, and
C6H5CH3 1.3 g. The system was then purged with ca. 1000
psi of carbon monoxide and then charged with 1500 psi of
carbon monoxide. The reactor was heated to 150C. at
which time the solution was agitated by means of rockiDg.
Upon completion of the experiment, 6.0 hours, the rocking
was stopped, the system cooled to 20-25C., the remaining
gas was vented, and the liquid contents isolated for
analysis. Vapor phase chromatographic data was obtained
on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1~ H3P04
on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 1.6 g and CH3C02CH3 28.9 g.
10 .
~~ 12,310
5~ ~ 3
Example 9
A 500 cc high pressure reactor equipped with a
glass liner was charged with the follow~ng: CH30H 56 g,
Mn2(C0)10 1.2 g, CH3I 6.8 g, 47% aq. HI 0.12 g. and
C6H5CH3 1.75 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi
of carbon monoxide. The reactor was heated to 150C. at
which time the solution was agitated by means of rocking.
Upon completion of the experiment, 7.0 hours, the rocking
was stoppèd, the system cooled to 20-25C., the remaining
gas was vented, and the liquid contents isolated for
analysis. Vapor phase chromatographic data was abtained
on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04
on 80/lO0 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 29.4 g, CH3C~2CH3 29.6 g and CH3C02H
4.8 g.
Example 10
A 500 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
Mn2(CO)10 1.6 g, CH31 1.0 g, 47% aq. HI 0.l2 g, and
C6H5CH3 1.0 g. The system was then purged with ca. 1000
psi of carbon monoxide and then charged with 1500 psi of
1:1 carbon monoxide:hydrogen. The reactor was heated to
120C. at which time the solution was agitated by means of
rocking. Upon completion of the experiment, 5.0 hours,
the rocking was stopped, the system cooled to 20-25C., the
remaining gas was vented, and the liquid contents isolated
~57~38 12,310
for analysis. Vapor phase chromatographic data was
obtained on an HP-5830 gas chromatograph equipped with
6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 29.7 g and CH3C02CH3 5.1 g.
Example 11
A 50Q cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
Mn2(C0)10 1.6 g, CH3I 2.0 g, 47% aq. HI 0.12 g, and
C6H5CH3 1.0 g. The system was then purged with ca. 1000
psi of carbon monoxide and then charged with 1500 psi 1:1
carbon monoxide:hydrogen. The reactor was heated to 120C.
at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking
was stopped, the system cooled to 20-25C., the remaining
gas was vented, and the liquid co~tents isolated for
analysis. Vapor phase chromatographic data was obtained
on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/170 H3P04
on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to
contain CH30H 20.5 g and CH3CO2CH3 13.0 g.
Example 12
A 500 cc high pressure reactor equipped with a
glass liner was charged with the following: CH30H 32 g,
Mn2(CO)10 1.6 g, RhCl~CO)(PPh3)2 ?0 mg, CH3I 1.0 g,
47% aq. HI 0.12 g, and C6H5CH3 1.0 g. The system was
12.
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~S7~338
was then purged with ca. 1000 psi of carbon monoxide and
then charged with 1500 psi 1:1 carbon monoxide:hydrogen.
The reactor was heated to 120C. at which time the solution
was agitated by means of rocking. Upon completion of the
experiment, 5.0 hours, the rocking was stopped, the system
cooled to 20-25C., the remaining gas was vented, and the
liquid contents isolated for analysis. Vapor phase chroma-
tographic data was obtained on an HP-5830 gas chromatograph
equipped with 6 ft x 1/8" stainless steel column packed
with 10% SP-1200/1% H3P04 on 80/100 Chromosorb ~/AW.
The final solution was analyzed and found to
contain CH30H 24.7 g and CH3C02CH3 8.4 g.
It was demonstrated in the carbonylation of
methanol that the rates of methanol carbonylation and
catalyst deacti.vation are both dependent on the ratio
of iodine to manganese. In a series of runs delineated in
Table I, it was demonstrated that for a given level of
manganese catalyst increasing the amount of iodide pro-
moter will increase both carbonylation and deactivation
until an iodine to manganese ratio of 8:1 is reached.
At this point an increase in the iodide promoter level
preferentially accelerates deactivation of the catalyst.
13.
12, 310
~3.57038
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14.
12,310
~L~L$7038
Although the invention has been described in
its preferred forms with a certain degree of particularity,
it is understood that the present disclosure of the
preferred forms has been made only by way of examples
and that numerous changes may be resorted to without de-
parting from the spirit and the scope of the invention.
