United States Patent (19) 11) 4,374,752

Argento et al. 45) Feb. 22, 1983

54 CATALYST AND PROCESS FOR THE 3,907,890 9/1975 Scanio ............................. 252/429 R
CONVERSION OF METHANOL TO 3,944,604 3/1976 Hershman et al. ............. 252/429 R
ACETALDEHYDE 3,966,595 6/1976 Gosser ............................ 252/429 R
4,151,208, 4/1979 Pretzer et al. .................. 260/601 R
75 Inventors: Benny J. Argento, South Charleston, 4,218,340 8/1980 Holmes ............. ... 252/429 R
W. Va.; Wellington E. Walker, 4,225,517 9/1980 Gane ................................... 568/487
deceased, late of Sissonville, W. Va.,
by Maxine M. Walker, executrix; FOREIGN PATENT DOCUMENTS
Rocco A. Fiato, Scotch Plains, N.J. 10373 4/1980 European Pat. Off. .
(73) Assignee: Union Carbide Corporation, 11042 5/1980 European Pat. Off. ............ 568/487
Danbury, Conn. 52-13611011/1977 Japan.
52-136111 11/1977 Japan.
21 Appl. No.: 279,158 1546428 5/1979 United Kingdom.
(22) Filed: Jun. 30, 1981 Primary Examiner-Arthur P. Demers
51 Int. Cl. ............ on a v 8 w 8 C07C 45/49; B01J 27/08 Attorney, Agent, or Firm-Francis M. Fazio
52 U.S. C. ............ a now 252/429 R; 568/487 (57) ABSTRACT
58) Field of Search a sa e o o os s. 568/487; 252/429 R A catalyst mixture is made with improved activity and
56) References Cited selectivity to acetaldehyde by using an inert diluent and
U.S. PATENT DOCUMENTS specifically defined concentrations of cobalt, a halide, a
3,091,644 5/1963 Aldridge ......................... 252/429 R trivalent phosphorus compound, and the inert diluent.
3,356,734 12/1967 Kuraishi.............................. 260/601 Use of the trivalent phosphorus compound significantly
3,625,755 6/1972 Potrafke ...... . . 252/429 R inhibits corrosion of the reactor metal.
3,681,021 8/1972 Mikovsky ... ... 252/429 R
3,808,246 4/1974 Fahey ......................... 252/429 RX 15 Claims, No Drawings
 1
4,374,752
2
the conditions often encountered in carbonylation, hy
CATALYST AND PROCESS FOR THE droformylation and homologation reactions, most hal
CONVERSION OF METHANOLTO ide promoted catalyst systems are corrosive towards
ACETALDEHYDE metal typically used in these systems leading to an unde
BACKGROUND OF THE INVENTION
sirably short life or the need to use expensive materials
that do not corrode as readily. It is, therefore, desirable
The present invention relates to a catalyst composi to provide a catalyst system that not only has acceptable
tion and to the related process for its use in the produc activity, selectivity and stability but one that is also less
tion of acetaldehyde by the hydroformylation of metha corrosive to the equipment.
nol with carbon monoxide and hydrogen. O The importance of employing catalyst systems con
The dwindling reserves of crude oil and the uncer taining specifically defined concentrations of compo
tainty of availablility of crude oil supplies has led to nents to minimize equipment corrosion and simulta
research for the exploitation of coal, natural gas and neously enhance activity, selectivity and stability has
other organic materials as the source of organic chemi not heretofore been recognized even though extensive
cals traditionally derived from petroleum. It is known 15 literature exists on the use of halide-promoted, cobalt
that these materials can be used to produce a gas mix based catalysts systems in the carbonylation, hydrofor
ture of carbon monoxide and hydrogen known as syn mylation, and homologation reactions involving synthe
thesis gas and that systhesis gas can be used to make SIS gas.
methanol, which can be further reacted through homol 20 Thus, in U.S. Pat. No. 3,356,734 issued to M. Kuraishi
ogation and hydroformylation reactions with more et al. on Dec. 5, 1967, there is disclosed a cobalt-iodide
synthesis gas in the presence of catalysts to produce catalyst system for the hydroformylation of methanol to
other chemicals. Among these other chemicals is acetal produce acetaldehyde. The process, however, exhibits
dehyde, an organic chemical compound of considerable low methanol conversions and low selectivity to acetal
importance as an intermediate in the production of, for dehyde, and there is no recognition indicated of the
example, ethanol, acetic acid, acetic anhydride, ethyl 25
corrosion problem, nor do they use a phosphorus com
acetate, butyraldehyde, and butanol as well as other pound or inert solvent in the reaction.
derivatives.
There are various catalyst systems known for use in In U.S. Pat. No. 4,151,208 issued to Pretzer et al. on
acetaldehyde-producing processes using the hydrofor Apr. 24, 1979, the catalyst system for the production of
mylation reaction, with many based on cobalt and using 30 acetaldehyde is cobalt(II) mesotetraaromaticporphine
a halide promoter. These catalyst systems can be judged and an iodine promoter. There is no reference to the use
on the basis of activity, selectivity, and stability (as of a phosphorus compound or an inert solvent, nor any
defined below). It is desirable that all of these values mention of the corrosion problem and its resolution.
remain high while minimizing corrosion of the equip Japanese Publications No. JA 77/136110 and JA
ment used; however, it is often true that an increase of 35 77/136111 both by Saito et al. and published on Nov.
one of these values will have a detrimental effect on one 14, 1977, disclose processes for making aldehydes using
or more of the others or increase the equipment corro catalyst systems containing cobalt, a halogen element
sion. Thus, a catalyst system that displays high values and a phosphorus compound. These processes exhibit
for activity, selectivity, and stability with minimal cor low selectivity towards acetaldehyde. There is also no
rosion would be an improvement over catalysts hereto recognition of the corrosion problem nor do they dis
fore disclosed. close the use of an inert solvent in the reaction.
"Activity' as used herein denotes the term that re , European patent application No. 10,373 by British
lates to the amount of reactants the catalyst can convert Petroleum Company Limited and published on Apr. 30,
per unit volume per unit time. The reactants being car 1980, discloses processes for making ethanol or acetal
bon monoxide, hydrogen and methanol. The activity 45 dehyde, using a catalyst system containing cobalt, an
can be determined by measuring the rate in which the iodide or bromide and a polydentate ligand wherein the
acetaldehyde product is made. It is important that the donor atoms are selected from nitrogen, phosphorus,
reaction be carried out at a sufficiently rapid rate for it arsenic, antimony and bismuth. The methanol may be
to be commercially acceptable. reacted with synthesis gas in the presence of an acid or
"Selectivity' as used herein denotes the amount of 50 acid derivative, or an inert liquid which is an aryl hal
desired organic products as opposed to other organic ide, a thiophene, a long chain acid or a silicon oil. The
by-products formed by the catalyzed reaction. In the predominant product is ethanol when the donor atoms
production of acetaldehyde, other organic by-products of the polydentate ligand are exclusively nitrogen or
are formed; the main such by-products being ethanol, phosphorus, particularly phosphorus. The predominant
methyl acetate and methane. 55 product is acetaldehyde when the donor atoms are
"Stability” as used herein denotes the length of time a exclusively arsenic, antimony or bismuth. There is no
catalyst will function before losing its catalytic activity. reference to the effect of the cobalt and halide catalyst
"Conversion' as used herein denotes percentage of components and the inert diluent nor is there reference
initially charged methanol converted to acetaldehyde to the effect of their relative concentrations on acetalde
and/or other organic products. 60 hyde selectivity or activity. This application teaches
"Realizable acetaldehyde' as used herein denotes the away from a catalyst system containing a phosphine and
sum of the free acetaldehyde produced plus the amount also having high selectivities and activities for acetalde
of acetaldehyde recoverable from 1,1-dimethoxyethane hyde. Particularly, this application shows no apprecia
formed during the reaction. tion for the necessity of using the entire combination; a
"Corrosion' as used herein denotes the gradual loss 65 source of cobalt, a halide, a phosphorus compound and
of weight or thickness of the materials of construction an inert diluent; at defined concentrations and ratios to
of the equipment or of the loss of structural integrity of obtain high activities and selectivities for acetaldehyde.
the walls thereof, during the course of the reaction. At There is also no teaching nor appreciation of the impor
 4,374,752
3 4.
tance of using a particular class of solvents, those con The catalyst and process of this invention show un
taining oxygen, to direct the reaction to acetaldehyde. usually high selectivity for the production of realizable
There is also no reference to the corrosion problem nor acetaldehyde in a completely unexpected system, one
to the effect of the process conditions on the acetalde containing a phosphorus compound. It was unexpected
hyde selectivity and activity for phosphorus-containing and unpredictable that the phosphorus containing sys
catalysts. There is also no mention of the corrosion tem of this invention would be selective to the produc
problem nor its solution. tion of acetaldehyde since British Pat. No. 1,546,428,
In British Pat. No. 1,546,428 to Slaugh, published on U.S. Pat. No. 4,225,517 and E.P.A. No. 10,373, dis
May 23, 1979 are disclosed catalyst systems similar to cussed above, all teach that such systems are selective to
those disclosed in the above referenced European Pa 10 ethanol. It has now been found that a catalyst system
tent Application No. 10,373. Disclosed is a process for containing trivalent phosphorus compounds and used
the preparation of ethanol by reacting hydrogen and with an inert diluent or cosolvent, provides for a cata
carbon monoxide in the presence of a cobalt catalyst, a lyst system that is highly selective toward acetaldehyde
hydrocarbon solvent, a halogen ion promoter, and ter and that has excellent activity and stability. It has also
tiary phosphine. The predominant product is ethanol, 15 been unexpectedly found that the use of a phosphorus
generally with significant amounts of other by-products compound significantly inhibits corrosion of the equip
such as acetic acid, methyl acetate and methane. There ment without deleterious effects on the catalyst activity
is no teaching showing the use of oxygen-containing or realizable acetaldehyde selectivity; in some instances
solvents or diluents to obtain high activities and selec improved activities and selectivities were noted.
tivities for acetaldehyde nor is there even disclosed the DESCRIPTION OF THE INVENTION
use of oxygen-containing solvents for any purpose. This invention is the improved catalyst system dis
There is also no recognition of the corrosion problem cussed above and its use in the hydroformylation reac
nor is there any teaching of its solution. tion of methanol with synthesis gas to selectively pro
In U.S. Pat. No. 4,225,517, issued Sept. 30, 1980 to duce acetaldehyde under conditions such that there are
Gane is disclosed a process for making acetaldehyde 25 experienced stability, activity, efficiency and corrosion
and ethanol. A process for making ethanol is disclosed benefits not heretofore achievable.
which uses a catalyst comprising an inert liquid, cobalt, The catalyst system contains four important compo
iodide or bromide and a compound containing nitrogen, nents that are present at specifically defined concentra
phosphorus, arsenic, or antimony. In this process, etha 30 tions and is employed under the reaction conditions
nol is the major realizable product. Also disclosed is a stated, all as more fully described and defined below.
process for making acetaldehyde using a system con There are present (a) a source of cobalt, (b) a source of
taining cobalt, an iodide or bromide, a compound con a halide, (c) a trivalent phosphorus compound and (d)
taining arsenic, antimony or bismuth and various other an inert oxygen-containing diluent. The catalyst system
additives. When triphenylphosphine is used in place of 35 must contain an inert diluent or solvent to obtain the
the arsenic, antimony or bismuth compound, ethanol is improved results of the invention. The advantages as
the major product. There is no disclosure of a phos above stated, in particular the improved selectivity and
phorus-containing catalyst that is highly selective to activity towards acetaldehyde and the improved corro
acetaldehyde, nor is there a disclosure that would lead sion properties are obtainable by using the components
one to such a catalyst. There is also no mention of the of the catalyst, the cobalt, the halide, the phosphorus
corrosion problem nor its solution. compound and the inert diluent, in the specifically de
None of the above references suggest or disclose the fined concentrations and ratios. The diluent must be an
importance of maintaining particular components of a oxygen-containing compound.
catalyst system; a source of cobalt, a halide, a phospho The cobalt component of the catalyst can come from
rus compound, and an oxygen-containing diluent or 45 a number of sources such as any of the known cobalt
solvent; at controlled concentrations and ratios so as to carboxylates, for example, cobalt formate, cobalt ace
enhance activity, stability and selectivity toward acetal tate, cobalt propionate, cobalt butyrate, cobalt benzo
dehyde while simultaneously minimizing equipment ate, cobalt valerate, cobalt hexanoate, and the like; the
corrosion, as is described in the description of our in known cobalt carbonyl compounds such as dicobalt
vention below. 50 octacarbonyl, cobalt tetracarbonyl hydride, compounds
SUMMARY OF THE INVENTION formed in situ such as methyl cobalt tetracarbonyl,
acetyl cobalt tetracarbonyl, and the like, or the phos
An improved catalyst and process for the hydrofor phine and/or halide substituted analogs of any of the
mylation reaction of methanol with synthesis gas to above, many of which are known to those skilled in the
produce acetaldehyde has been found. High activity 55 art; cobalt oxide and cobalt hydroxide; cobalt-carbonate
and selectivity to the desired acetaldehyde are possible and cobalt bicarbonate; the soluble cobalt halides such
in a system which is stable and which unexpectedly and as cobalt iodide, cobalt bromide and cobalt chloride;
unpredictably shows reduced corrosion towards com and cobalt. Cobalt may also be supplied as a supported
mon materials of construction, such as Hastelloy (R) B, form such as on a silica, alumina, or polystyrene support
Hastelloy (R) C or 316 stainless steel. The improved 60 or on any one of the supports known in the art. Cobalt
process comprises reacting methanol with carbon mon silicate, cobalt titanate, and cobalt orthotitanate and the
oxide and hydrogen in the presence of a catalyst system like are also suitable sources of cobalt. A convenient
comprising a source of cobalt, a source of a halide, a source of cobalt is cobalt(II) acetate tetrahydrate.
trivalent phosphorus containing compound and an inert The halide component can be any halide except fluo
diluent wherein the relative concentrations of catalyst 65 ride. Preferably the halide is bromide or iodide, most
system components and methanol are maintained within preferably iodide. If iodide, the halide can be supplied
specifically and critically defined ranges as explained iodine or any of its derivatives. Illustrative of suitable
below. compounds one can mention, acetyl iodide, potassium
 4,374,752
5 6
iodide, sodium iodide, lithium iodide, calcium iodide, alcohols such as ethanol, n-propanol, n-butanol, isobuta
ammonium iodide, methyl ammonium iodide, tetraethyl nol, n-pentanol, and n-hexanol; secondary alcohols such
annonium iodide, methyl ammonium iodide, tetra as isopropanol, 2-pentanol and 3-pentanol; cyclic alco
methyl ammonium iodide, triphenylphosphonium io hols such as cyclopentanol, polyols such as 1,4-
dide, tricyclohexylphosphonium iodide, cobalt iodide; butanediol, 2,5-hexanediol and polytetramethylene
hydrogen iodide; the alkyl iodides having from 1 to 10 ether glycol (Polymeg 1000 (trademark)); ketones such
carbon atoms such as methyl iodide, ethyl iodide, pro as acetone, methyl ethyl ketone, 2,5-hexanedione, cy
pyl iodide, 2-ethylhexyl iodide, n-decyl iodide, or any clopentanone, and cyclohexanone; ethers such as die
other source of iodide which will ionize to form iodide thylether, tetrahydrofuran, 2,5-dimethyltetrahydrofu
ions in the reaction medium. One can also employ any 10 ran and diphenyl ether. Also suitable are mixtures of
other organic compound that will furnish iodide to the two or more of the above. Water can also be used as a
reaction medium. Further, one can use mixtures of io diluent in small amounts or in a mixture with one or
dine and/or iodide compounds, if so desired. more of the above. A high volume of water can lead to
The trivalent phosphorus compounds are the phos undesirable by-products; therefore, the system prefera
phines of the formula: 15 bly contains a small amount of water. About 10 volume
PR3 percent of water in the total reaction system has been
found suitable. About 75 volume percent of water has
and the polydentate phosphines of the formula: been found unsuitable. Since water is a reaction by-pro
20
duct in the formation of acetaldehyde, water is likely to
be present in the reaction system in any case, particu
larly when the continuous reaction mode is used. Some
RN P----P1 R other compounds, like water, cannot be used in a high
R1 H
" NR volume but can be in a mixture or in a small amount in
25 the catalyst system. These include ethylene glycol, 1,4-
butane diol, 2,4-pentane dione, diethylene glycol, N
wherein each R group taken individually is similar or methyl pyrolidinone, propylene glycol and tripropyl
different, and is; (a) a saturated or unsaturated, linear or phosphine oxide. The above list of suitable diluents is
branched alkyl group having from 1 to 20 carbon atoms, not to be considered all inclusive since any known suit
preferably 4 to 10 carbon atoms (b) an aryl, aralkyl, or able inert diluent or solvent can be used possessing the
alkaryl group having from 6 to 10 ring carbon atoms, 30
preferably 6 ring carbon atoms; or (c) a saturated or characteristics discussed above. Usually the preferred
inert diluents or solvents are those which form mono
unsaturated cycloalkyl having from 5 to 8 ring carbon phase systems and are essentially unreactive during the
atoms preferably 5 to 6 ring carbon atoms or (d) when reaction.
two such R groups are attached to the same phosphorus In the practice of the invention the concentrations
atom and taken together, they are a saturated or unsatu 35
rated divalent alkylene group having from 4 to 10 car and ratios of the constituents of the catalyst system are
as follows:
bon atoms preferably 4 to 6 carbon atoms; and n is an (1) The volume ratio of inert solvent or diluent to
integer having a value of 2 to 10, preferably from 2 to 6. methanol charged should be from 0.3:1 to 20:1 prefera
Any of the known phosphorus compounds can be used bly from 0.5:1 to 8:1.
and illustrative thereof one can mention triethylphos (2) The cobalt is present at a concentration of from 1
phine, tributylphosphine, triphenylphosphine, tri-(4-
methoxyphenyl)phosphine, tri-p-tolylphosphine, tris(3- to 40 milligram-atoms of cobalt per gram-mole of meth
chlorophenyl)phosphine, diphenylhexylphosphine, anol charged, preferably from 3 to 15 milligram-atoms
dimethyl(3-methoxyphenyl) phosphine, dibutylstearyl per gram-mole of methanol.
phosphine, tribenzylphosphine, cyclohexylidibutylphos 45 (3) The halide is present at a halide to cobalt milli
phine, tricyclohexylphosphine, propyl diphenylphos gram-atom ratio of 1:1 to 10:1, preferably greater than
phine, dipropyl phenylphosphine, ethyl dipropylphos 2:1 and most preferably from 2:1 to 6:1.
phine, bis(diphenylphospino) ethane, bis(diethylphos (4) The phosphorus compound is present such that
phino)propane, bis(disphenylphosphino)butane and the the phosphorus to halide milligram-atom ratio is from
like. The phosphine compounds can also contain sub 50 0.1:1 to 2.8:1, preferably from 0.4:1 to 2:1.
stituents that do not unduly interfere with the reaction. As previously indicated unexpectedly improved re
Any inert diluent which contains oxygen and is not sults are achieved when specifically defined concentra
unduly reactive with the other constitutents in the reac tions and ratios are employed in the catalyst system.
tion system and which does not unduly interfere with Ethanol is not primarily produced as is disclosed in the
the reaction can be used. Also any oxygen-containing 55 above discussed British Pat. No. 1,546,428, U.S. Pat.
diluent that may react in the system but forms products No. 4,225,517 and E.P.A. No. 10,373, but rather unex
that do not unduly interfere with the reaction is suitable. pectedly acetaldehyde is selectively produced as the
Among the diluents for use in the invention are the predominant product, in a system containing a trivalent
polyalkylene glycols, excepting di-ethylene glycol, that phosphorus compound in the specified ratios. These
have from 2 to 350 ethyleneoxy or propyleneoxy units 60 surprising results are obtained by carefully controlling
or mixtures of such units in the molecule and are liquid the composition of the catalyst system. It has been
under reaction conditions, the alkyl or aryl or cycloal found that the combined effect of maintaining the cata
kyl monoethers or di-ethers of the polyalkylene glycols lyst constituents within the above defined ratios pro
having from 2 to 350 ethyleneoxy or propyleneoxy units vides significantly improved performance, with selec
or mixture of such units in the molecule as well as the 65 tivity to realizable acetaldehyde higher than that re
mono-ethers or di-ethers of ethylene glycol or propy ported in the prior art discussed above.
lene glycol, 1,4-dioxane, sulfolane, tripropylphosphine The improved selectivities and activities of the inven
oxide, and methyl acetate. Also suitable are primary tion are also improved by preferably maintaining the
 4,374,752
7 8
process conditions in defined ranges discussed below; pressured to about 3,000 psig with synthesis gas. With
i.e. the mole ratio of hydrogen to carbon monoxide in agitation (about 750 rpm), the reactor contents were
the synthesis gas and the temperature, and the pressure. heated to the indicated temperature over a period of
Therefore, in the acetaldehyde forming process of the about 45 minutes whereby the pressure increased. When
invention, the mole ratio of hydrogen to carbon monox- 5 the temperature had been reached, the reactor was
ide in the synthesis gas, or other synthesis gas-forming brought to the desired pressure plus about 250 psig with
compositions used, is generally from 0.2:1 to 10:1, pref synthesis gas. The reaction was allowed to consume gas
erably from 0.25:1 to 5:1, most preferably from 0.5:1 to until the pressure had fallen to about 250 psig below the
1.5:1. desired pressure. The reactor was then repressurized.
The reaction is generally carried out at a temperature 10 One such cycle was considered a 500 psig synthesis gas
of from about 120° C. to 250 C., preferably from about uptake. Unless otherwise specified, reactions were al
16O C. to 225 C. lowed to proceed until the indicated psig gas uptake had
The pressure used is generally from 1,000 psig to occurred. The operating pressure reported in the exam
10,000 psig, preferably from 1,500 psig to 6,000 psig, ples was the desired pressure for the run. At the end of
Further, it has also been observed that corrosion of an experiment, the reactor contents were normally
the equipment was diminished to an unexpected and cooled to 10° C. A vapor phase sample was taken and
unpredictable extent. This is due in large part to the use analyzed for CO, H2, CO2, and CH4 plus other gaseous
of the phosphorus compound, in the catalyst system components using gas-liquid chromatography. The re
contained in the defined amounts. The discovery that actor gas phase was then vented through two dry ice
corrosion is reduced under these conditions is of signifi acetone traps. The reaction was pressurized three times
cant importance in view of the costs involved in erect with 90 psig nitrogen and vented through the same trap
ing a new facility and in replacing corroded parts. system.
The improved results of the invention are not due to The liquid reactor contents were dumped into a
one factor alone but due to the combined effect of the 25 chilled pressure bottle and crown capped and analyzed.
defined catalyst composition i.e. the cobalt concentra To analyze the liquid phase samples a Hewlett-Packard
tion, the halide to cobalt milligram-atom ratio and the Model 5880 gas chromatograph was employed having
phosphorus to halide milligran-atom ratio, the inert two columns, inch by 20 feet in size and packed with
diluent present in the defined amount; and also in part to 60/80 mesh Chromosorb 101 (E) (a polyvinyl styrene).
the process conditions as defined, i.e., the hydrogen to 30 Each column was made from two 10 ft lengths con
carbon monoxide molar ratio, the temperature and pres nected in series with a inch union.
St. Values for selectivity and rate of production are for
In a typical practice of the invention on a laboratory realizable acetaldehyde or in other words the figures
scale, the autoclave is cleaned, the liquid reactants, also include 1,1-dimethoxyethane, commonly known as
catalyst compounds and diluents are charged into the is dimethyl acetal, on a contained acetaldehyde basis.
autoclave after which the solid components are Dimethyl acetal is formed as a result of the acetalde
charged, the reactor is closed, purged with synthesis gas hyde product combining with methanol in the reactant
and then pressurized with synthesis gas. With agitation mixture and is readily converted back to acetaldehyde
the pressurized contents are heated to the desired tem and methanol.
perature and then additional synthesis gas is added to 40 The selectivity values are calculated by dividing the
the desired pressure plus 250 psig. The reaction is per weight of acetaldehyde by the total weight of reaction
mitted to proceed until sufficient gas has reacted such products. Included in the weight of acetaldehyde is
that the pressure has fallen 250 psig below the desired dimethyl acetal on a contained acetaldehyde basis. Val
pressure. The reaction is then repressurized to the de ues for rate of production of acetaldehyde also include
sired pressure plus 250 psig and the reaction continued. 45 dimethyl acetal on a contained acetaldehyde basis.
One such cycle is considered 500 psig gas uptake. The EXAMPLE I
cycles are continued for a set period of time or until the
desired gas uptake (generally about 3,000 psig) has oc A series of expirements was carried out as described
curred. It is generally undesirable to continue the reac above with a gas uptake of 3,000 psig, and a reactor
tion for a excessively long time, since with long reaction 50 pressure of 5,000 psig (E250 psig). The initial charge to
times condensation products of higher molecular the reactor consisted of 112.5 ml of the diethylether of
weight form as impurities. In laboratory batch reac diethylene glycol, 37.5 ml of methanol, 8 mmol of co
tions, reaction times of from 5 minutes to 4 hours have balt acetate tetrahydrate, 14 mmol of iodine and, 30.8
been found suitable. At the conclusion of the reaction, mmol of triphenylphosphine. The temperature, and
the reactor contents are cooled and the vapor phase is 55 hydrogen to carbon monoxide molar ratio are shown in
analyzed and vented. The liquid contents of the reactor Table I. The results of these experiments are also shown
are then removed and analyzed. in Table I. The selectivities are in weight percent and
The following examples serve to further illustrate the the product rate in [Link]/l/h. Selectivity and rate for
invention. realizable acetaldehyde includes the sum of acetalde
In the batch procedure used in the examples below, 60 hyde and dimethyl acetal on a contained acetaldehyde
prior to charging the catalyst, diluent, and methanol, basis. The realizable acetaldehyde production rate and
the laboratory autoclave reactor was washed with selectivity are significantly higher than those found in
methanol at 100° C. at from 400 to 1,000 psig synthesis the prior art. Also the rates and selectivities of ethanol
gas pressure for 30 minutes. The reactor was drained, and other by-products are much smaller than those
opened, rinsed with acetone, and dried with nitrogen. 65 found in the prior art. This example demonstrates how
To the open and cleaned reactor there were charged through practice of the invention, a product comprising
first the liquid and then the solid components. The reac predominately realizable acetaldehyde is made with
tor was closed, purged with synthesis gas and then only small amounts of ethanol and other by-products.
 4,374,752
9 10
TABLE I
Selectivity (Weight Percent) '. Rate (gnol?/hr)
Run H2/CO Temp AcH DMA Rel. AcH EtOH MeOAc CH4 Rel. AcH EtOH Chí
l 1.S 170 69.9 20.4 89.3 1.9 6.3 1.4 4.9 0.11 0.24
2 1.5 190 71.5 18. 88.0 0.2 4.4 3. 6.5 0.21 0.68
3 1.5 205 70.3 16.6 84.0 4.2 2.7 6.1 6.3 0.32 1.35
4. 1.0 205 74.5 11.1 84.0 3.7 6.4 4.2 0.2 0.4S 1.46
AcH = Acetaldehyde
DMA = dimethyl Acetal
Rel. AcH = Realizable Acetaldehyde
Etoh = Ethyl Alcohol
MeOAc = MethylAcetate

EXAMPLE II acetaldehyde and also the rate of production of realiz

able acetaldehyde as gram moles per liter per hour.
A series of experiments was carried out as described In run 11 there was 4.0 mmol cobalt acetate tetrahy
above at a temperature of 170° C., a gas uptake of 3,000 drate, 14.0 mmol iodine, and 30.8 mmol triphenyl phos
psig, a reactor pressure of 5000 psig (250 psig) and a phine. The other conditions were as in the previous
H2/CO molar ratio of 1.5:1. The initial charge to the S.
reactor consisted of 112.5 ml of the diethylether of 20 On runs 2, 3, and 8 diluents were used that should not
diethylene glycol, 37.5 ml. of methanol, 4 mmol of co be used in large amounts; therefore, the high rates and
balt acetate tetrahydrate and 7 mmol of iodine. The selectivities characteristic of the practice of the inven
specific phosphorus compound used in each run and its tion are not shown in these runs. The other runs show
quantity are shown in Table II. Also shown for realiz how one can obtain the high selectivities and activities
able acetaldehyde are the weight percent selectivity and possible by practice of the invention.
the production rate as gram moles per liter per hour. 25 TABLE III
The realizable acetaldehyde is the sum of the free acet
aldehyde produced plus the amount of acetaldehyde - Realizable Acetaldehyde
Production
recoverable from the dimethyl acetal formed during the Rate Gas
reaction. In Run 11 the source of the phosphorus com 30 Wt. Percent (g mol/ Uptake
ponent was polystyrene containing 6.2 weight percent Run Diluent Selectivity 1/h) (psig)
triphenylphosphine bound thereto, the amount used 1 DEDEG 90.6 4.00 3000
was sufficient to provide 2.95 milligram-atoms phos 2 Tripropylphosphine oxide 45.5 0.12 900
phorus to the reaction. For the various phosphorus-con 3 N-methyl pyrolidinone 25.7 0.10 2250
4, 1.2-Dimethoxybenzene 73.7 3.40 3000
taining additives the results show a very favorable ac 5 18-Crown-6 Ether 79.8 1.00 3000
tivity for acetaldehyde as shown by the production rate 3 6 Diphenyl Ether 90S .60 3000
of acetaldehyde. 7 Sulfolane 702 1.00 3000
8 Diethylene Glycol 29.5 0.11 3000
TABLE II 9 Triethylene Glycol 66.7 1.10 3000
Realizable Acetaldehyde 10 2-Methyl Pentanediol-2,4 65.6 0.27 3500
11 DBDEG 89.0 2.7 3000
Production 40
Ph2P(CH2)PPh2 Selectivity Rate DEDEG = Diethylether of diethylene glycol
Run R3POmmol) (mmol) (wt %) (gmol/l/hr) DBDEG = Dibutyl ether of diethylene glycol
1 R = phenyl --- 81.6 2.
(7.7) EXAMPLE IV
2 R = p-tolyl --- 73.5 1.9
(7.7) 45 A series of experiments was carried out as described
3. R = cyclo- - 88.0 2.8
hexyl(7.7) above using various diluents at a temperature of 170° C.,
4 -- n = 203.85) 78.8 1.7 a reactor pressure of 5000 psig (-250 psig), a H2/CO
5
6
---
-
n
n
= 2(7.7)
= 3(3.85)
85.4
87.4
1.6
.6
molar ratio of 1.5:1 and with 3000 psig gas uptake. The
7 - n = 4(3.85) 77.3 1.9 50
initial charge to the reactor consisted of 120 ml. of the
8 - n = 5(3.85) 79.2 2.2 diluent, 30.0 ml. of methanol, 4 mmol of cobalt acetate
9 - n = 6(3.85) 78.1 1.9 tetrahydrate, 8 mmol of iodine and 8 mmol of triphenyl
10 R = phenyl n = 2(1.925) 77.0 2.2 phosphine. The specific diluent used in each run is
(3.85) shown in Table IV as are the weight percent selectivity
11 R = phenyl - 72.2 2.2
Ph = phenyl 55
for realizable acetaldehyde, the production rate of real
izable acetaldehyde as gram mole per liter per hour, and
the reaction time. The mixture of run 4 was 90 ml
EXAMPLE III methyl acetate, 6-ml ethyl acetate, 12-ml n-propanol,
A series of experiments using various diluents (runs and 6-ml n-butanol. All the runs shown good selectivity
and rate for realizable acetaldehyde for the different
1-11) was carried out as described above at a tempera- 60 diluents used.
ture of 170° C., a reactor pressure of 5000 psig (t:250 TABLE IV
psig) and a H2/CO molar ratio of 1.5:1. The initial
charge to the reactor consisted of 112.5 ml. of the dilu Acetaldehyde
ent, 37.5 ml. of methanol, 4 mmol of cobalt acetate Production Wt. Percent Reaction
Rate Selectivity Time
tetrahydrate, 9.0 mmol of iodine, and 19.8 mmol of 65 Run Diluent (gmole/1/h) Acetaldehyde (h)
triphenylphosphine. The specific diluent used in each 1 OMEG 1.37 89.4 1.
run, its quantity, and the gas uptake are shown in Table 2 DMDEG 2.97 68.5 0.7
III as are the weight percent selectivity for realizable 3 Methyl Acetate 0.6 68.5 2.0
 4,374,752
11 12
TABLE IV-continued selectivity to acetaldehyde at various halide to cobalt
Acetaldehyde milligram-atom ratios and phosphorus to halide milli
Production Wt. Percent Reaction gram-atom ratios.
Rate Selectivity Time TABLE VI
Run Diluent (g mole/1/h) Acetaldehyde (h) 5
4 Mixture 0.63 80.9 1.8 Realizable Acetaldehyde
5 DMTEG 4.1 84.2 0.8 I-/Co P/I- Production Wt. Reaction
DMEG = Dimethyl ether of ethylene glycol mg-atom ng-atom Rate Percent Time
DMDEG = Dimethyl ether of diethylene glycol Run ratio ratio (gmol/l/h) Selectivity h)
DMTEG as dimethylether of tetraethylene glycol O 1 2.5 0.55 2.2 77.6 0.97
2 2.5 1. 2.9 87.7 03
3 2.5 1.5 2.4 87.0 1.32
EXAMPLE V 4. 2.5 1.9 2.0 90.9 .4
This example shows how an oxygen-containing dilu 5 3.5 0.55 E.8 80.2 0.95
6 3.5 1.1 3.5 93.8 0.92
ent may be used to increase the acetaldehyde selectivity 7 3.5 1.5 3.0 92.2 O
to a surprisingly high extent. A series of experiments 15 8 3.5 1.9 .8 88.5 .2
was carried out as described at 5000 psig (E250 psig); 8 9 4.5 0.55 3.6 84.4 0.87
mmol of cobalt acetate tetrahydrate and 16 mmol of 10
1.
4.5
4.5
.
5
4.1
2.8
87.7
80.8
D.85
1.03
iodine were in the initial charge for runs 1 to 4. For runs 12 4.5 1.9 1.4 912 t.8
1 to 2 there was no diluent and 150 ml of methanol only 13 5.5 0.55 3.3 86.4 ).97
was used in the initial charge to the reactor, in runs 3 20 14 5.5 . 3.4 88. 0.87
and 4 112.5 ml. of 1,4-dioxane and, 37.5 ml. of methanol 5 5.5 1.5 3.0 87.0 .97
were used. The weight percent selectivity for realizable 16 5.5 .9 0.3 88.2 .0
acetaldehyde, the production rate of realizable acetalde 7
18
3.5
3.5
O
O
1.7
1.5
70.3
71.1
.3
.2
hyde as gram moles per liter per hour, the reaction time,
and gas uptake are shown in Table V. The results indi 25
cate that the use of a diluent can increase both the activ
ity and selectivity of the catalyst system to acetalde EXAMPLE VII
hyde. A series of experiments at various P/I ratios was
TABLE V carried out at a temperature of 170° C., a pressure of
Realizable Acetaldehyde
30 5,000 psig (+250 psig), a gas uptake of 3000 psig and a
Production H2/CO mole ratio of 1.5:1. The initial charge to the
Rate Wit. Reaction reactor contained 112.5 ml of the diethylether of dieth
H2:CO Molar Uptake
Ratio (psig)
(g mole/ Percent
Selectivity
Time ylene glycol, and 37.5 ml of methanol with 4.0 mmol of
1/h) (h) cobalt supplied as cobalt acetate tetrahydrate. The io
15 4750 0.48 43.9 4.0 35 dide was supplied as iodine and the phosphorus as tricy
2.5 26.50 0.35 44. 6.0 clohexyphosphine. Production rate and selectivity of
1.5 4000 2.14 87.4 1.3
2.5 2500 152 82.6 1.2 realizable acetaldehyde are shown in Table VII for
"no diluent used various phosphorus to iodide gram-atom ratios. The
--diluent used
40
results shown the unexpected and surprisingly high
selectivity towards acetaldehyde obtainable through
EXAMPLE VI practice of the invention.
TABLE VII
A series of experiments at various I/Co and P/I- Realizable Acetaldehyde
gram-atom ratios was carried out at a temperature of
i 170° C., a pressure of 5,000 psig (E250 psig) and a 45 I-/Co P/I-
mg-atom ng-atom
Production
Rate
Wt.
Percent
Reaction
Time
H2/CO molar ratio of 1.5:1. The initial charge to the Run ratio ratio (gmol/1/h) Selectivity th)
reactor contained 112.5 ml. of the diethylether of dieth 3.5 0.55 1.2 83.8 .93
ylene glycol, 37.5 ml of methanol, and 4 mmol of cobalt 2 3.5 l, 5 83.9 E.03
acetate tetrahydrate. The iodide was supplied as iodine 50 3 3.5 1.5 1.2 80.4 .33
and the phosphorus as triphenylphosphine. The gas 4. 3.5 1.9 0.76 76.9 3.18
uptake was 3,000 psig except run 16 which was 880 psig,
In Table VI there are shown the reaction time, the
selectivity in weight percent of realizable acetaldehyde EXAMPLE VIII
and the production rate for realizable acetaldehyde in A series of experiments at various P/I ratios was
gram-moles per liter per hour for various I/Co and 55
P/I ratios. The outcome of these experiments show carried out at a temperature of 170° C., a pressure of
that at these ranges of I/Co and P/I-milligram-atom 5,000 psig (h:250 psig) and a H2/CO ratio of 1.5:1. The
ratios within the scope of the invention result in a high gas uptake was 3,000 psig except for run 5 which was
rate and selectivity. Comparison of runs 4-8 runs at 3080 psig, The initial charge to the reactor contained
various phosphorus to halide gram-atom ratios with 112.5 ml of 1,4-dioxane, and 37.5 ml of methanol with
runs 17 to 18 run under similar conditions but with no 4.0 mmol of cobalt supplied as cobalt acetate tetrahy
phosphorus compound shows how use of a phosphorus drate. The iodide was supplied as iodine and the phos
compound can increase both activity as shown by the phorus as triphenyl phosphine. Production rate and
production rate and also selectivity towards acetalde selectivity of realizable acetaldehyde are shown in
hyde. A completely surprising result, since as discussed 65 Table VII for various phosphorus to iodide gram-atom
above, the prior art teaches that ethanol is the predomi ratios.
nant product when phosphorus compounds are used. Comparison of phosphorus-free run 1 showing a low
The data also shows acceptable production rate and selectivity to acetaldehyde with the other runs showing
 13
4,374,752
14
the high selectivity obtainable by practice of the inven A second series (II) of eight companion experiments
tion using a phosphorus compound shows how the was conducted at the same conditions as the first series
selectivity to acetaldehyde is substantially increased using the same initial reactor charges except that tri
using a phosphorus compound in the catalyst system. phenylphosphine was incorporated in the charge to
TABLE VIII 5 give a phosphorus to iodide milligram atom ratio of
Realizable Acetaldehyde 0.50. Corrosion test coupons of metal compositions
I-/Co P/I- Production Wt. Reaction typical of high pressure reactors used in reactions of this
mg-atom mg-atom Rate Percent Time type were placed in the high pressure reactor during
Run ratio ratio (g mol/1/h) Selectivity (h) 10 each of the eight runs of each series.
1 3.5 O 0.54 58.5 2.50
2 3.5 0.55 2.2 82.9 1.32 TABLE X
3 3.5 1. 2.1 86.1 1.52. Cobalt Acetate Iodine Methanol
4. 3.5 1.5 1.6 82.2 1.95 Run Tetrahydrate (mg) (mmol) (ml) Diluent
5 3.5 1.9 0.43 76.2 4.0
1 1.0 1.0 30 1,4 dioxane
15 2 1.0 4.0 30 1,4 dioxane
3 1.0 5.0 30 1,4 dioxane
EXAMPLE IX 4. 1.0 20.0 30 1,4 dioxane
5 4.0 1.0 75 DMTEG
A series of experiments at various Co concentrations 6 4.0 4.0 75 DMTEG
and I/Co and P/I ratios was carried out at a temper 7 4.0 5.0 75 DMTEG
ature of 170° C., a pressure of 5,000 psig (+250 psig), a 20 8 4.0 200 75 DMTEG
gas uptake of 3000 psig and a H2/CO mole ratio of 1.5:1. DMTEG = Dimethyl ether of tetraethylene glycol.
In the initial charge to the reactor there were 112.5 ml
of the diethylether of diethylene glycol and 37.5 ml of The average corrosion rates were determined by loss
methanol and 4.0 mmol of cobalt supplied as cobalt of thickness of the coupons and thereby calculating the
acetate tetrahydrate. The iodide was supplied as iodine 25 annual rate of loss of the thickness.
and the phorphorus as triphenylphosphine. Production
rate and selectivity of realizable acetaldehyde as shown
in Table IX for various amounts and ratios of cobalt, Corrosion Rate (inches/yr)
iodide and phosphorus. Some of these runs are operated Coupon Metal Series Hastelloy B (E) Hastelloy C(R)
in the non-preferred ranges of the I/CO and P/I milli- 30 (I) Phosphine Free 0.0670 0.0390
gram-atom ratios and thus do not show the highest (II) Phosphine Added 0.008 0.005
selectivity and activity obtainable by practice of the
invention. However comparison of these runs with run
4 with I/CO milligram-atom ratio outside of the scope theThese standard corrosion rate analyses indicate that
catalyst mixtures containing the phosphine com
of the invention will show either a higher production 35 pounds, as disclosed
rate or a higher selectivity of realizable acetaldehyde cantly less corrosive into the present invention, are signifi
these metals than are the compa
for the runs without the scope of the invention. rable phosphine free catalyst mixtures.
TABLE IX The same compositions in previous examples are
Cobalt 40 shown here as having superior anti-corrosion proper
Acetate Realizable Acetaldehyde ties. Thus is demonstrated how one by practice of this
Tetra- I/Co P/I- Wit. Production invention can achieve high activity and selectivity for
hydrate mg-atom mg-atom Percent Rate
Run (immol) ratio ratio Selectivity (g mol/1/h) acetaldehyde and yet provide for lower corrosion rates.
1 4.0 5.5 1.9 0.35 73.7 45 Tests were also run using corrosion test coupons of
2 4.0 7.0 1.5 0.39 72.2 316 stainless steel. The results of these tests showed
3 4.0 9.5 1. 1.0 69.8 much lower corrosion rates than is normal in halide
4. 4.0 9. 0.55 0.45 49.5 promoted systems. This is significant since it is well
5 40 2.5 2.3 0.59 73.9
6 4.0 2.5 2.7 '0.10 60.2 known that halide promoted cobalt catalysts are very
7 4.0 3.5 2.3 0.21 68.1 corrosive to 316 stainless steel and for this reason 316
8 4.0 3.5 2.7 0.10 60.9 50 stainless steel has, heretofore, been an unacceptable
9 3.0 2.0 0.4 0.75 58.9
O 3.02.0 2.0 0.87 73.9 material for process equipment used in halide-promoted
3.0 1.0 0.4 0.58 6.0 catalyst systems. However, through practice of the
2 3.0 1.0 2.0 1.27 70.8 instant invention corrosion of this and other materials is
13 15 2.0 0.4 1.90 85.
14 15 2.0 2.0 2.90 65.3 55 significantly reduced to a point allowing substantial
15 5 1.0 0.4 .74 51.6 economic benefit.
16 15 1.0 2.0 2.0 60.2 The data in the above examples shows the surpris
ingly high activity, and selectivity to realizable acetal
dehyde and the improved corrosion properties ob
EXAMPLE X 60 served when using the phosphine-containing catalyst
This example illustrates the superior anticorrosion compositions of the present invention.
properties of the catalyst of the invention. What is claimed is:
A first series (I) of eight phosphine-free experiments 1. A catalyst system for the production of acetalde
was run at a temperature of 140 C., a pressure of 4,000 hyde by the reaction of methanol, carbon monoxide and
psig (+250 psig) and at a H2/CO molar ratio of 1.2:1. 65 hydrogen, which catalyst comprises (I) a source of
The combined volume of the methanol and the diluent cobalt, (II) a source of iodide or bromide, (III) an inert
was 150 ml. Table X summarizes the conditions of each oxygen-containing diluent, and (IV) a trivalent phos
of these runs. phorus compound of the formula:
 4,374,752
15 16
H
Rn R
Rn H YR PR3 or P- C P
Y
PR3 or P C P R1 " N.
H

wherein each R group taken individually is similar or wherein each R group taken individually is similar or
different, and is; (a) a saturated or unsaturated, linear or O different, and is; (a) a saturated or unsaturated, linear or
branched alkyl group having from 1 to 20 carbon atoms, branched alkyl group having from 1 to 20 carbon atoms,
or (b) an aryl, aralkyl, or alkaryl group having from 6 to (b) an aryl, aralkyl, or alkaryl group having from 6 to 10
10 ring carbon atoms, or (c) a saturated or unsaturated ring carbon atoms, or (c) a saturated or unsaturated
cycloalkyl having from 5 to 8 ring carbon atoms, or (d) cycloalkyl having from 5 to 8 ring carbon atoms, or (d),
5 when two such R groups are attached to the same phor
when two such R groups are attached to the same phos phorus atom and taken together a saturated or unsatu
phorus atom and taken together, a saturated or unsatu rated divalent alkylene group having from 4 to 10 car
rated divalent alkyl group having from 4 to 10 carbon bon atoms; and wherein n is an integer from 2 to 10, the
atoms; and wherein n is an integer from 2 to 10, and diluent to methanol volume ratio is from 0.3:1, to 20:1,
wherein the inert diluent to methanol volume ratio is 20 the cobalt concentration is from 1 to 40 milligram-atoms
from 0.3:1 to 20:1, the cobalt concentration is from 1 to of cobalt per gram-mole of methanol charged, the hal
ide to cobalt milligram-atom ratio is from 1:1 to 10:1,
40 milligram-atoms of cobalt per gram-mole of metha and the phosphorus to halide milligram-atom ratio is
nol charged, the halide to cobalt milligram-atom ratio is from 0.1:1 to 2.8:1, the hydrogen to carbon monoxide
from 1:1 to 10:1; and the phosphorus to halide milli 25 mole ratio is from 0.2:1 to 10.1.
gram-atom ratio is from 0.1:1 to 2.8:1. 8. The process of claim 7 wherein each R group taken
2. The catalyst of claim 1 wherein each R group taken individually is similar or different, and is a (a) a satu
individually is similar or different, and is; (a) a saturated rated or unsaturated, linear or branched alkyl group
having from 4 to 10 carbon atoms (b) an aryl, aralkyl, or
or unsaturated, linear or branched alkyl group having alkaryl group having 6 ring carbon atoms, or (c) a satu
from 4 to 10 carbon atoms (b) an aryl, aralkyl, or alkaryl 30 rated or unsaturated cycloalkyl having from 5 to 6 car
group having 6 ring carbon atoms, or (c) a saturated or bon atoms, or (d), when two such R groups are attached
unsaturated cycloalkyl having from 5 to 6 ring carbon to the same phosphorus atom and taken together, a
atoms, or, (d) when two such R groups are attached to saturated or unsaturated divalent alkylene group having
the same phosphorus atom and taken together, a satu 35 from 4 to 10 carbon atoms; and wherein n is an integer
from 2 to 6.
rated or unsaturated divalent alkylene group having 9. The process of claim 7 wherein the diluent to meth
from 4 to 10 carbon atoms; and wherein n is an integer anol volume ratio is from 0.5:1 to 8.1 cobalt concentra
from 2 to 6. tion is from 3 to 15 milligram-atoms of cobalt per gram
3. The catalyst of claim 1 wherein the diluent to mole of methanol charged, the iodide or bromide to
methanol volume ratio is from 0.5:1 to 8.1, the cobalt cobalt milligram-atom ratio is from 2:1 to 10:1 the phos
concentration is from 3 to 15 milligram-atoms of cobalt phorus to halide milligram-atom ratio is from 0.4:1 to
2:1.
per mole of methanol charged, the iodide or bromide to 10. The process of claim 9 wherein the iodide or
cobalt milligram-atom ratio is from 2:1 to 10:1, and the 45 bromide to cobalt milligram-atom ratio is from 2:1 to
phosphorus to halide milligram-atom ratio is from 0.4:1 6:1.
to 2:1. 11. The process of claim 7 wherein the trivalent phos
4. The catalyst of claim 3 wherein the iodide or bro phorus compound is triphenylphosphine.
mide to cobalt milligram-atom ratio is from 2:1 to 6:1. 12. The process of claim 7 wherein the trivalent phos
phorus compound is tricyclohexylphosphine.
5. The catalyst of claim 1 wherein the trivalent phos 50
13. The process of claim 7 wherein the hydrogen to
phorus compound is triphenylphosphine. carbon monoxide mole ratio is from 0.2:1 to 10:1, the
6. The catalyst of claim 1 wherein the trivalent phos temperature is 120° C. to 250 C. and the pressure is
phorus compound is tricyclohexylphosphine. from 1,000 psig to 10,000 psig,
7. A process for the production of acetaldehyde by 55 14. The process of claim 13 wherein the hydrogen to
the reaction of methanol, carbon monoxide and hydro carbon monoxide mole ratio is from 0.25:1 to 5:1, the
gen wherein the reaction is catalyzed by cobalt and an temperature is from 160° C. to 225 C. and the pressure
is from 1,500 psig to 6,000 psig.
iodide or bromide promoter in the presence of an inert 15. The process of claim 14 wherein the hydrogen to
oxygen-containing diluent and a trivalent phosphorus 60
carbon monoxide mole ratio is from 0.5:1 to 1.5:1.
compound of the formula: k se

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 4,374,752
DATED : 2-28-83
NVENTOR(S) : B. J. Argento, W. E. Walker, R. A. Fiato
It is certified that error appears in the above-identified patent and that said Letters Patent
is hereby Corrected as shown below:

Column 13, in Table IX the values for Run lo,

in the five columns used to report the data,
should read as follows to correspond to the
original specification
COLUMN
RUN l 2 3 4. 5
O 3. O 2. O 2. O O. 87 73.9

signed and sealed this

Twenty-sixth Day of April 1983
SEAL
Attest:

GERALD J MOSSNGHOFF
Attesting Officer Commissioner of Aotents and Trademarks
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 4,374,752
DATED 2/28/83
NVENTOR(S) B. J. Argento, W. E. Walker, R. A. Fiato
It is certified that error appears in the above-identified patent and that said Letters Patent
is hereby Corrected as shown below:
Column 13, Table IX, the headings at the tops of the last
two columns should be interchanged so that the fifth heading
becomes the last heading and the last heading becomes the
fifth heading in the Table; they will appear in the following
order:

Production Wit.
Rate Percent
(g. mol/l/h) Selectivity
signed and Scaled this
Twenty-sixth Day of July 1983.

GERALD J. MOSSINGHOFF
Attesting Officer Commissioner of Patents and Tradenarks