United States Patent Of?

ce

3,450,735
Patented June 17, 1969

3,450,735

scope of this invention are those wherein the aluminum

is bonded to a primary carbon atom, that is, a carbon

PRODUCTION OF ALUMINUM TRIALKOXIDE

AND ALIPHATIC ALCOHOLS
Allan J. Lundeen and James E. Yates, Ponca City, Okla,
assignors to Continental Oil Company, Ponca City,
Okla., a corporation of Delaware
No Drawing. Filed Nov. 14, 1966, Ser. No. 593,698

atom having attached thereto two hydrogen atoms, and

include such compounds wherein the carbon content of
the alkyl radicals varies from 2 to 30 canbon atoms or
even more. Although theoretically there is no limit to the
number of carbons in the alkyl radical that can be used,
we generally prefer to employ a trialkylaluminum com

Int. 'Cl. C07f 5 / 06'

US. Cl. 260-448

7 Claims

ABSTRACT OF THE DISCLOSURE

pound wherein the carbon content of alkyl radicals varies

10 from 2 to 22. Obviously the alkyl radicals of the trialkyl
aluminum compound may be the same or di?erent. If a

compound is used wherein the alkyl radicals are the same,

one alcohol is produced. If, on the other hand, a com
pound is used wherein the alkyl radicals are diiferent, a

During the oxidation of trialkylaluminum compounds

with oxygen, isopropanol is added to suppress the forma

tion of side products. Acetone subsequently formed is re 15 mixture of alcohols is formed.

moved by heating.
For example, triethylaluminum can be oxidized to alu
minum ethoxide in the presence of isopropanol and eth
anol obtained by hydrolysis of the aluminum ethoxide.
This invention relates to an improved method for the
Similarly, tripropylaluminum, tributylaluminum, tripen
production of aluminum trialkoxide compounds and pri 20 tylaluminum, and trihexylaluminum can be oxidized in
mary aliphatic alcohols. More particularly, it relates to
the presence of isopropanol to the corresponding alumi
the production of primary aliphatic alcohols by the oxi
num propoxide, aluminum butoxide, aluminum pentoxide,
dation of trialkylaluminum compounds and subsequent
and aluminum hexoxide, and by hydrolysis the corre
hydrolysis of the resultant aluminum al'koxide com

pounds.

sponding alcohols, propanol, butanol, pentanol, land

25 hexanol, can "be obtained. Other trialkylaluminum com

Various methods have been proposed for producing

primary aliphatic alcohols. A comparatively recent proc
ess for synthesizing these alcohols has been based on the

oxidation of tri-alkylaluminum compounds to form alu

pounds which can be employed are triisobutylaluminum,

, trioctylaluminum, tri-(2-ethylhexyl)-aluminum, tridodec

ylaluminum, trioctadecylaluminum, ethylbutylhexylalu

minum, and the like.

minum alkoxides which are then hydrolyzed to form al 30

Particularly useful for oxidation and subsequent con
cohols. This process has not heretofore been entirely sat
version to the primary aliphatic alcohols is the mixture

istactory because of the formation of by-products and the

of trialkylaluminum compounds known as growth prod
resultant lower yield of the desired alcohols. US. Patent
uct which is obtained by the well known growth reaction
3,257,468 discloses that the yield of a primary alcohol
in which a low molecular weight mono-ole?n, such as
obtained by the aforedescribed process can be improved 35 ethylene, propylene, butene, etc., is combined with a low
by carrying out the later stages of the oxidation in the
molecular weight aluminum trialkyl, such as, for exam
presence of an aluminum alcoholate derived from a
ple, an aluminum trialkyl having the alkyl substituents
secondary alcohol, particularly, aluminum isopropoxide.
containing from about 2 to 24 carbon atoms. The result
ant growth product comprises a trialkyl compound in
The aluminum alcoholate is added when the oxidation
40
is no more than two-thirds complete. This method has
which the alkyl groups vary widely in molecular weight.
resulted in improved yields of alcohol, but its application
The preparation of growth product is discussed in a num
is restricted in that the aluminum alcoholate must be
ber of US. patent, including US. Patent 3,249,648. The
composition of a typical growth product is presented in
added when the oxidation reaction is no more than two
Table I.
thirds complete. Use of the aluminum alcoholate com
45
pound also increases the cost of the process.
TABLE I
An object of this invention is to provide an improved
Composition of a growth product
process for the production of aluminum alkoxides.
Alkyl_ group of trialkyl
Another object of this invention is to provide an im
Mole percent
proved process for the production of primary aliphatic 50 aluminum compound:
in growth product
alcohols.
c2 __________________________________ __ 1.83
Another object is to provide a more economical proc

ess for the manufacture of primary aliphatic alcohols.

Further objects and advantages will become apparent

from the following description.
55
Brie?y, we have discovered an improved process for
preparing aluminum trialkoxide compounds and primary
aliphatic alcohols which comprises conducting the latter
stages of the oxidation of trialkylaluminum compounds
with molecular oxygen to aluminum alkoxide compounds 60
in the presence of a quantity of added isopropanol. We
prefer to add the isopropanol when oxidation of alumi
num trialkyls to the trialkoxide compounds is between
about 80 to about 90 percent complete. However, the ad
dition of isopropanol can be made when oxidation is only 65
70 percent complete or can be delayed until oxidation is

about 100 percent complete. Acetone, generated during

the reaction after addition of isopropanol, subsequently is

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C16

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14.65
19.54
19.54
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oz,

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0.02

Mean number of moles of ethylene added per mole of

trialkylaluminum=4.00.

As to the oxidizing agent, it may be air, enriched air,

pure oxygen, etc.

removed and, as in the prior art, the alcohol is obtained

by hydrolyzing the aluminum alkoxides. The acetone re 70 As discussed in US. Patent 3,257,468, the oxidation
of the trialkylaluminum compounds to the aluminum alk
moved can be hydrogenated to isopropanol and recycled.
oxides is not quantitative; but certain by-products are also
The trialkylaluminum compounds included within the

obtained, some in a relatively high yield. These by-prod

3,450,735
3

dized and hydrolyzed to alcohols is growth product ob

tained from the reaction of aluminum triethyl and ethyl

ucts include carbonyl compounds (for example, alde

hydes), esters, and hydrocarbons but are not limited to
those only, as other by-products also may be produced.
While we do not wish to be bound by any theory as to
how these by-products are formed, we believe that the
following is a correct explanation.
The oxidation of aluminum alkyls is believed to be a

ene.

A~quantity of growth product in an inert paraf?nic hy

drocarbon diluent is placed in a reactor vessel. Air, oxy
gen, or other oxygen containing gas is bubbled through
the mixture of growth product and inert diluent. The tem
perature of the exothermic reaction is controlled by con

two-step process involving reactions of the type indicated

by Equations 1 and 2.

tinually circulating a portion of the reacting mixture

through a cooling loop or coil. The effluent gas from the

10 reaction can :be monitored for oxygen content and the

appearance of carbonyl compounds in the reaction mix

Evidence supporting this mechanism has been published

ture monitored by testing samples in infrared adsorption

in the literature. In addition, the oxidation of other metal

equipment.

When oxidation of the growth product is determined

organic compounds such as Grignards and boron alkyls 15
through analysis of the e?iuent gas to be between 70 and
involves reactions similar to (1) and (2).
100 percent complete (or preferably between 80 and 90
The formation of aldehyde and hydrocarbon from the
percent complete), or when the appearance of carbonyl
peroxide intermediate of reaction (1), if the Al-OO
compounds is indicated by infrared adsorption measure
radical is bonded to a primary carbon atom, can be ex
plained by assuming that a portion of the peroxide inter 20 ments, isopropanol is added to the reactor. The quantity
added is equal to between about 0.5 and about 20 percent
mediate undergoes thermal decomposition as indicated by
by weight (or preferably between about 5 and about 10
the following reactions. In these reactions the
percent by weight) of the weight of growth product

If

originally added to the reactor. Oxidation is then com

R--CII

radical is the equivalent of the R radical of reaction (1),

R being an alkyl radical. The R alkyl radicals of reaction
(1) are not to be considered as all necessarily identical.

25

pleted.
When oxidation of the growth product to the equivalent
trialkoxide product is completed, the mixture of aluminum
trialkoxides, inert diluent and any other compounds is

either retained in the reactor or transferred to another

30 vessel where, in either instance, it is heated at a rate and

to a temperature that will permit controlled evolution of

acetone and excess isopropanol from the mixture. If ace

tone is allowed to remain too long in the mixture, un

wanted side products can form from it. It is, however,

equally important to allow su?icient time for the isopro

35 panol to react with aldehydes and aldehyde precursors

present in the reaction mixture. Although heating is a

preferred method of vaporizing and removing acetone and
isopropanol, other methods of removal are possible such
as bubbling an unreactive gas through the reaction mix

ture, adsorption, or stripping.

When the acetone and excess isopropanol have been
removed from the mixture of aluminum alkoxides, diluent,
and side products, the mixture is treated to recover the

aluminum alkoxides, for example by spray stripping.

The recovered aluminum alkoxides then are hydrolyzed

and the resulting hydrolized product is fractionated into

fractions containing normal aliphatic alcohols of gradu
ated molecular weights.
Pilot plant tests have demonstrated the working of our
invention. In these tests growth product of a composi

If the aldehyde of reaction (5) is not removed, it will

tion similar to that in Table I was oxidized and con

of aldehydes, ketones, other carbonyl-containing products,

verted to alcohols. In each of the tests, about 80 gallons

of growth product mixed with an inert hydrocarbon
diluent was placed in a reactor and oxidized by bubbling
air through the mixture. Pressure in the reactor during
oxidation was about 40 p.s.i.g.; the temperature during
the ?rst 30 to 40 percent of oxidation was about 96 F.
and during the remainder of the oxidation was about
90 F. Isopropanol was added when continual infrared

sponding increase in the yield and quality of the desired

This point varied between 83 and 92 percent completion

alcohol. We do not know why improved results are

tained by the use of isopropanol; it may be that the
propanol chemically reduces some intermediate in
aldehyde forming process or the aldehyde itself. The

ob
iso
the
im

of the oxidation reaction. After oxidation was com

pleted, the oxidation mixture was ?rst heated under a pres

portant fact is that the presence of the isopropanol effects

the increased yield of alcohol. This is particularly sur

sure was raised to 150 mm. of mercury and the tempera

undergo a further reaction to yield an ester (Tischtschenko

reaction) and unsaturated carbonyl containing-compounds

(aldol condensation) giving, ultimately, a complex mix
ture comprising an alcohol, ester, aldehyde, hydrocarbon,
unsaturates, etc.

We have found that the presence of isopropanol dur

ing the later stages of the oxidation reduces the amount

and other by-products in the ?nal product with a corre 60 analysis indicated the appearance of carbonyl compounds.

prising since normally isopropanol and the partially oxi

dized aluminum trialkyl would be expected to react direct
ly and to form saturated hydrocarbons.
The method of our invention can be applied either to
a batch process for the manufacture of aluminum trialk
oxide and normal aliphatic alcohols or to a continuous
process. We will ?rst describe it as applied to a batch proc
ess in which the trialkylaluminum compound to be oxi

sure of 100 mm. of mercury to a temperature of 130 to

140 F. When most of the acetone was removed, the pres

ture increased to 160 F. Finally, the pressure was reduced

to 50-100 mm. of mercury and the temperature raised to
250-300" F. to remove the last of the isopropanol.

After this step, the mixture of oxidized growth product

and solvent was stripped in a two-stage stripper. The over

head product from the stripper constituted diluent and

any by-products formed. The bottom product recovered
and removed from the stripper constituted relatively pure

3,450,735

aluminum trialkoxide which was then hydrolyzed with

sulfuric acid, neutralized with caustic, and water-washed

plished in several ways, one consisting of ?owing the tri

alkylaluminum through a contact tower in a ?ow path op
posite that of a stream of oxygen-containing gas thereby

The crude alcohol product thus obtained was then frac

tionated into several cuts comprising a butanol-water cut,

alcohols containing 6, 8, and 10 carbon atoms, alcohols

containing 12 and 14 carbon atoms, alcohols containing

partially oxidizing the trialkylaluminum. A desired amount

of isopropanol is then continuously mixed with the e?luent
partially oxidized trial-kylaluminum and the oxidation

16 and 18 carbon atoms, and the residual bottoms con

taining alcohols of 20 or more carbon atoms and other

completed in a second contact column. Optionally the

isopropanol can be added in the ?rst column at a point in

high boiling point residue. Each of the alcohol cuts was

the lower part of the column and oxidation completed
then hydrogenated, a standard ?nishing step which im
10 in the ?rst contact column. The oxidized growth product
proves the quality of the alcohol.
can then be passed to a vacuum stripping column wherein
Two control tests, A and B, were made in which no

the acetone and excess isopropanol are removed over

isopropanol was added to the growth product during oxida

head; the aluminum trialkoxide removed from the bottom
tion. T-wo tests, C and D, were made in which 1 pound of
is passed to a second stripping column where the carrier
isopropanol was added during oxidation for each 10 15 liquid is removed. The oxidized trial'kylaluminum can then
pounds of growth product placed in the reactor. One
be further treated and hydrolyzed to alcohol.
run, E, was made in which 0.5 pound of isopropanol was
Reasonable variation and modi?cation are possible
added during oxidation for each 10 pounds of growth
within the scope of the foregoing disclosure and the ap
product placed in the reactor. \In tests C and D the per
pended claims to the invention, the essence of which
cent increase in the yield of normal alcohols of 6 to 18 20 comprises, in the oxidation of trialkylaluminum com
carbon atoms per molecule averaged 5.4 percent; cor
pounds to the corresponding aluminum trialkoxides, the
respondingly, in- test E a 2.8 percent yield increase of
addition to the reaction of a quantity of isopropanol equal
C6 to C18 alcohols resulted. The addition of 1 pound of
to between about 0.5 and 20 .weight percent of the tri
isopropanol per 10 pounds growth product caused an
alkylaluminum compound reacted, when said oxidation
average decrease of 22 weight percent in the loss of ma 25 is between about 70 and 100 percent complete.
terial to the residual bottoms containing alcohols of 20
We claim:
or more carbon atoms per molecule. This was signi?cant
1. A process for converting aluminum alkyl com
in that this decrease of weight of residual bottoms (a less
pounds containing 2 to 30 carbon atoms in each alkyl
desirable and valuable fraction) represents an increase
group to aluminum alkoxide compounds, comprising:
in the yield of the more valuable lower molecular weight 30
(a) partially oxidizing the aluminum alkyl compounds

alcohols. A 5 weight percent reduction in the amount of

with oxygen;
material lost to the overhead product in the stripping
(b) adding isopropanol to the resulting partially oxi
process also resulted.
dized aluminum alkyl compounds;
In addition to increasing the yield of alcohols having
(c) completing the oxidation reaction; and
6 to 18 carbon atoms per molecule, the' quality of the 35
(d) removing acetone and excess isopropanol from the
alcohol product was improved. The alcohol fractions ob
oxidation reaction product obtained.
tained from the run using 1 pound of isopropanol per 10
2. The process of claim 1 wherein the isopropanol
pounds of growth product were analyzed and compared
is added in an amount of between about 0.5 and about
with the corresponding alcohol fractions obtained with
20 weight percent of the aluminum alkyl compounds ini
out the isopropanol treatment. The proportion of undesir
tially present at the beginning of the oxidizing step of (a).
able carbonyl compound, esters, and unsaturated com
3. The process of claim 1 wherein the isopropanol
pounds was reduced considerably as shown in Table II.
is added in an amount of between about 5 and about 10
Table II correlates the number of carbon atoms per
weight percent of aluminum alkyl compound initially pres
molecule of alcohol with the ratio of moles of carbonyl
ent at the beginning of the oxidizing step of (a).
compound, ester, and unsaturated compounds present in 45
4. The process of claim 1 wherein the isopropanol is
alcohols derived from the process using isopropanol ad
added When the oxidizing step of (a) is between about 70
and 100 percent complete.
dition to the moles of these same undesired compounds
in alkohols derived from the process using no isopropanol.
5. The process of claim 1 wherein the isopropanol is
added when the oxidizing step of (a) is between about 80
TABLE II.AVERAGE RESULTS FOR 10 WEIGHT PERCENT
ISOPROPANOL ADDITION
50 and about 90 percent complete.
6. The process of claim .1 wherein said step (d) of re
Carbon
Moles carbonyl
Moles ester
Moles unsaturate
No. of

alcohol

(ICaOH)/Mo1es

carbonyl (control)

0. 86
0. 56
0. 56
0. 42

moving acetone is accomplished by heating the oxidation

(ICaOH)/Mo1es (IC3OH)/Mo1es un

ester (control)

saturate (control)

0.86
1. 32
0. 95
0. 28

0. 93
0. 74
0. 32
0. 38

reaction product to a temperature su?icient to volatilize

55

acetone present in said product.

7. The process of claim 1 wherein said aluminum alkyl
compounds contain 2 to 22 carbon atoms in each alkyl
group.

In the fraction containing alcohols of more than 20

carbon atoms per molecule and other residual com

pounds, the fraction of the total alcohol was increased

from 76 percent to 84 percent. The lfraction of normal 60
alcohols present was increased from 57 percent to 77

percent, by weight.
When the method of our invention is applied to a

continuous process for manufacturing aluminum tri

alkoxide, the trialkylaluminum compound, for example,

65

growth product in a suitable carrier liquid, is continu

References Cited
UNITED STATES PATENTS
3,017,438 1/ 1962 Atwood.
3,104,251
9/1963 Foster et al.
3,257,468 6/1966 Dickey et al.

TOBIAS E. LEVOW, Primary Examiner.

H. M. S. SN EED, Assistant Examiner.

ously contacted with a stream of oxygen or oxygen-con

taining gas to oxidize the trialkylaluminum compound to

the desired point of partial oxidation. This can be accom

US. Cl. X.R.

70

260-632