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Патент USA US2383579

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Aug. 28, 1945.
H. D._ALLEN ET AL
~
2,383,579
PROCESS FOR TREATING FATS AND FATTY OILS
Filed March 30, 1943
STEAM
COOLING
.
WATER
PRESSU RE
CONTROL
PREHEATER
CONDENSER
REACTION COIL
ALCOHOL
FLAS H
CHAMBER
STEAM
ALCOHOL
ACID
(CAUSTIC
SODA)
MXXING
CHAMBER
ESTERS
SALT FILTER
I
INVENTORS
HAROLD DWAINE ALLE N
WILLIAM ASHLEY KLI_NE
BY
‘
ATTORNE
Patented Aug. 28, 1945
_ 2,383,579
UNITED‘ STATES PATENT OFFICE
raoonss FOR 'rarghigo
2,383,579 FATS AND FATTY
Harold Dwaine Allen, Glen Rock, and William
Ashley Kline, Morris Plains, N. J ., assignors to
Colgate-Palmolive-Peet Company, Jersey City,
N. J ., a corporation of Delaware
'
Application March 30, 1943, Serial No. 481,080
18 Claims. (Cl. 260-4109)
The present invention relates to a process for '
completion desired in a single hot contacting of -
the materials, or, as disclosed by Joseph Henry
the alcoholysis of fatty materials and, more par
Percy in United States patent application Serial
ticularly, to animproved- high temperature proc—
No. 462,369 (?led October 17, 1942) -, the glycerides
ess for reacting fatty glycerides with alcohols,
whereby fatty acid esters and glycerine are pro (.1 may be partially esteri?ed with the alcohol in a
?rst treatment to form a pool of partially reacted
duced in a relatively short time.
material containing monoglycerides and diglycer
The methods of alcoholysis or radical inter
ides,‘ so that the reaction mixture is substantially
homogeneous. The partial esteri?cation may be
scribed by the prior art have had certain dis
advantages, especially in continuous operation. 10 accomplished by keeping the glyceride and the
alcohol in contact in a pool at moderate or at ele
Thus, theltime required for a reaction between
vated temperatures for a time interval ‘insum
the alcohol and the fatty glyceride to provide sat
cient for the reaction to go to completion under
isfactory yields of vfatty ester and glycerine ‘on
the operating conditions, as by continuously run
an industrial scale varied in the case of alkaline
ning fatty glyceride, alcohol and catalyst into a
alcoholysis from about twenty minutes toseveral
pool or mixing chamber and continuously with
hours and usually ran about thirty minutes to
drawing a substantially equivalent amount of par
an hour, and when using an acidic catalyst var- tially reacted material at a rate designed to main
led from about three hours to about twenty
tain uniform conditions in the pool. The reac
hours. This not only tied up equipment and
stock-in process but, in operating continuously by 20 tion of the constituents of the withdrawn mate
rial is then brought toward completion at a tem
passing the reactants together through a reaction
peratureoabove the normal boiling point of the
coil, it was necessary to provide a reaction coil of
alcohol involved and at a pressure which keeps
relatively great length if satisfactory yields were
an alcohol liquid phase. It may be preferred at
to be produced.
this point, when using an alkaline catalyst, to
It is an object of the present invention to ‘pro
add suf?cient acid to decompose any soap formed
vide an improved process for reacting fatty glyc
from the catalyst, and in certain cases, especially
erides (or other fatty acid ester of a higher alco
when alcohols higher than methanol are em
hol) with an alcohol to produce fatty esters and
ployed in the process, the appearance of two
glycerine (or other higher alcohol) in high yield
phases does not occur until after acidi?cation
in a relatively short time.
or removal of unreacted alcohol‘.
It is also an object of the invention to provide a
While the phases may be separated, with or
novel continuous process for producing a high
without acidi?cation, before removal of the excess
yield of fatty esters and glycerine from fats and
’ alcohol, it is generally preferred to vaporize un
fatty oils in relatively inexpensive and space
reacted alcohol prior to settling, as disclosed by
conserving equipment.
'
Walter Russell Trent in United States patent ap- '
Other objects and advantages of the invention
plication Ser. No. 462,370 (?led October 1'7, 1942) . .
will be apparent from the following description,
After removal of the alcohol, the residue is al
taken in conjunction with the accompanying
lowed to settle; glycerine separates out as a lower
drawing, wherein:
‘layer and is withdrawn, and the upper layer con
The ?gure represents a flow diagram illustrat
taining alkyl esters, and in some cases incom
ing the ?ow of materials in the operative steps of
pletely reacted glycerides, is also removed for
a process in accordance with this invention.
further processing. Various ways of treating the
According to the present invention, a fatty acid
upper layer, which comprises the esteri?ed mate
ester of a higher'alcohol (e. g., a glyceride) is
contacted with an alcohol, preferably in the pres 45 rial, have been pointed out in application Ser. No.
change between a glyceride and an alcohol de
ence of an alcoholysis catalyst.
The mixture is
heated to a temperature above the normal boil
ing point of the alcohol, and a pressure suf?cient
to preserve a liquid alcohol phase is maintained.
A very rapid reaction takes place, with formation
of alkyl esters and the higher alcohol (say. glyc
erine) in a relatively short time. Unreacted al
cohol is removed, and the products are separately
recovered.
»
'
_ The reaction may be brought to the degree of 55
462,369.
In one procedure in accordance with the pres
ent process, the fatty glyceride is premixed with
an alcohol and a catalyst and is passed through a
contactor coil.
There the mixture is heated to a '
temperature above the boiling point of the alcohol
but below its critical temperature and below the
temperature of substantial degradation of the
materials. Sufficient back pressure is applied to
_maintain a substantial proportion of the alcohol
2
2,383,579
in the‘llquid state. The mixture remains in the
contactor coil for a relatively short time, say of
the order of up to about ten minutes for alkaline
alcoholysis and up to about thirty minutes when
using an acidic catalyst, and is then run to a
preheater, where it is heated under substantially
atmospheric pressure to a temperature su?icient
to volatilize the excess alcohol. The resulting
liquid-vapor mixture is passed into a separating
chamber from which the volatilized unreacted al
cohol is withdrawn and preferably passed to a
A similar pressure is applied in ethanolysis at
100° 0., although at this temperature an even
lower pressure would'keep substantially all of the
ethyl alcohol in the liquid state. As the reaction
temperature rises, higher pressures are required,
a suitable pressure for reaction with methanol at
about 125° C. being of the order of 150 pounds
per square inch absolute.
.
The reaction mixture leaves the coil and, if
necessary, may then be heated to volatilize the
excess alcohol, with or without prior neutraliza
tion. Where the reaction mixture contains un
converted catalyst and is not neutralized before
condenser and receiver. The remaining material
comprises alkyl esters and glycerine, which are
separately recovered. This may be accomplished
the excess alcohol, it is advantageous
by codistillation and settling the distillate or by 15 volatilizing
to carry out such volatilization below the tem
running'the material directly into a settling tank.
perature of substantial reversal of the reaction
The glycerine separates out as a lower layer and
upon removal of the alcohol. In general, the op
is withdrawn, and the esters (and glycerides, if ,
eration may be carriedout at reduced pressures,
present) are also removed. The process or any
at atmospheric pressure, or at supertamospheric
step thereof may be carried out in batch, inter 20 pressures.
mittent orcontinuous operation.
The fatty material treated by the process may
In general, the fatty oil,.,alcohol,and catalyst
be any of the natural fatty acid esters, such as
maybe premixed in a homogenizer at about room
the fats and fatty oils suitable for employment
temperature before being run into the reaction
coil. When carrying out the alcoholysis with an 25 by the soap-makingart in any of the processes
heretofore known, or any other fatty acid ester
alkaline catalyst, it is preferred thus- to. mix the
of a higher alcohol, such as glycerol or other poly
reactants at a moderate-temperature if small
hydric alcohols or long-chain (say, about twelve
amounts of water are present, in order to avoid .
to about twenty carbons) monohydric alcohols,
the possibility of excessive local saponi?cation of
.ormixtures'of these esters, especially glycerides
the resulting esters. Such saponi?cation removes
the catalyst from the reaction body before the 30 offatty acids having about eight to about twenty
six, and preferably about twelve to about twenty,
reactants have been thoroughly mixed and al—
carbon atoms per molecule of fatty acid. These
lowed'to react. When using an acid catalyst or
esters
includes coconut oil, palm oil, olive oil, cot
when, even with an alkaline catalyst, the react
tonseed oil, corn oil,- tung. oil, soya bean oil, wool
ants are substantially anhydrous, the oil and the
fat, tallow, whale and ?sh oils, etc. Although a
alcohol may be separately preheated’ to the de
re?ned oil containing substantially no moisture
sired reaction temperature and thoroughly mixed
is preferably employed, as the presence of water '
directly in the reaction coil, whereby the reaction
decreases the yield of esters in alkaline alco
can be completed in an extremely short reaction
time. In the presence of an alkaline catalyst 40 holysis and slows down the reaction when an acid
catalyst is used, small amounts of water can be ' ‘
andJof-small amounts of water, preheating and
hot contacting tend to decrease the yield of esters,
The reaction coil is heated to provide tempera-_ 'tures above the boiling point of the alcohol at
atmospheric pressure, say to a temperature of
about 80° C. to about 160° C. or higher, but below
the temperature of substantial degradation of the
materials. Where an alkaline catalyst is em
ployed, this may also be below the temperature
of substantially complete removal of the alkaline 50
catalyst by saponi?cation of the resulting esters.
However, a. temperature may be employed which
will produce high ester and glycerine yields in a
very short and practical reaction time with simul
taneous conversion of the alkaline catalyst to 55
tolerated when, carrying out the reaction with
the lower alcohols, such as methyl or ethyl alco
hol and especially methanol.
Similarly, Where
acid alcoholysis is employed or where, in alkaline
alcoholysis, acidi?cation of the reaction mixture,
is contemplated, either before or after volatilize.
tion of the unreacted alcohol, free fatty acid may
be present in the glyceride in the proportion of
10% to 20% or even higher.
In carrying out the alcoholysis according to
this invention, short-chain aliphatic monohydric
alcohols, including aryl-substituted aliphatic al- I
cohols, are preferably employed, particularly the
saturated, primary alcohols, especiallyalcohols
having a boiling point in the presence of water
in excess of the azeotropic composition of lower
ticular temperature for a given combination of
than
100° C. at atmospheric pressure and, more
reactants. In acid or alkaline alcoholysis with
particularly, the lower alcohols having one to
either methanol or ethanol, it is preferred to
maintain temperatures of about 80° C. to about 60 about six carbon atoms per molecule. Thus, al
cohols satisfactory for use in forming esters with
160° C., and temperatures of about 90°‘ C. to about
soap. This yield will be a maximum at a par
130° C. have given particularly satisfactory re
sults.
The mixture in the reaction coil is kept under
'
a pressure su?icient to maintain a liquid alcohol 65
phase.
If desired, the pressure may be low
enough to permit the volatilization of a portion
the fatty acid components of the glycerides treat
ed include such low molecular weight monohydric
alcohols as methyl alcohol, ethyl alcohol, propyl
alcohol, isopropyl alcohol, n-butyl alcohol, iso
butyl alcohol, secondary butyl alcohol, tertiary
butyl alcohol, the amylk alcohols, benzyl alcohol,
etc. While any proportion of fatty material and
alcohol may be used, it is preferred to employ an
amount of alcohol at least about 50% in excess
‘ amount of alcohol volatilized in the coil is rela 70
of the calculated theoretical amount necessary
tively low- Thus, at a reaction temperature of
for alcoholysis of the particular glycerides treat?
100° C. for methanol, it is preferred to employ a
ed, and particularly satisfactory results have been '
gauge pressure of 55 pounds per square inch or
obtained when using an excess of at least three
of the alcohol during the reaction, but, in general,
e?iciency of operation is improved when the
higher, say about '75 pounds per square inch,
?ve times the stoichiometric amount required.
whereby the alcohol is substantially unvaporized. 75 to In
selecting an alcoholysis catalyst. an alkaline
2,888,579
I or anacidic catalyst may be employed. vAmong
those which have been found suitablefor use in
the present process are sodium hydroxide, sodium
101° C. and 103° C." A su?icient back pressure is
maintained upon the coil to prevent volatilization
of the alcohol. The coil is equipped with outlet
cocks at various points therealong for the pur
pose of withdrawing'the material after any de
methylate, sodium carbonate, barium oxide, lime,
tetramethyl ammonium hydroxide, boron tri?uo
ride, aluminum chloride, hydrochloric acid, tri
sired interval of reaction time. After 3.1 min- ‘
chloracetic acid, phosphoric acid, glycerine mono
acid sulphate, sulphuric acid, organic sulphonic
acids, alkyl sulphuric acids, etc. While- it is pos
sible to obtain good yields with proportions of 10
utes in the coil, a portion of the reaction mixture
is withdrawn-and promptly acidi?ed with dilute
sulphuric acid to halt the reaction. The acidi?ed
mixture is allowed to settle, and a'lower glycerine
catalyst up to about 0.30 mol per equivalent of
layer is withdrawn. The upper layer is washed
fatty glycerides and higher, it is preferred to use
with water to remove unreacted alcohol, residual
large excesses. of alcohol and to introduce rela
glycerine and excess mineral acid, and it is then
tively small amounts of catalysts, say of the order
dried and vacuum distilled. An ester. yield of
of about 0.03 mol to about 0.10 mol per equivalent
approximately 96.2% of the calculated theoreti
of glycerides. A convenient way of introducing
cal yield is obtained.
the catalyst into the reaction mixture is in ad
A second portion of the reaction mixture is re
mixture with and, where practical, advanta
moved from the reaction coil after an additional
geously in solution in the alcohol employed. In
4.1 minutes and is treated in a manner similar to
alkaline alcoholysis, when the glyceride treated 20 the treatment of the ?rst portion. A yield of
contains free fatty acid, su?icient alkalinecata
methyl esters equivalent to about 96.5% of the
lyst is added to provide an excess of alkali above
calculated theoretical yield is obtained.
that destroyed by the free fatty acid present.
Example III
After acidi?cation with an acid stronger than the
fatty acid of the glyceride, the fatty acid goes
into the ester layer. However, acid catalysts are
25
particularly appropriate for use with oils contain
ing a large proportion of free fatty acids, as the '
acids are esteri?ed during the process.
The following examples illustrate the present
invention, but it will be understood that the in
vention is not limited thereby.
. Example I
1 Using the same proportions of cottonseed oil, '
methanol and sodium hydroxide as set forth in
Example 11, the materials are mixed and run into
a reaction coil, as there described. The mixture
is heated in the coil to a temperature of 131° C.
30 and is maintained at a pressure suf?cient to keep
the alcohol in the liquid state. A portion of the
reaction mixture is withdrawn from the reaction
coil after 3.1 minutes therein and, after treat
ment ‘as described in Example II, gives a yield of
About 224 c. e. per minute of re?ned anhydrous 35 96.8% of methyl esters of cottonseed oil fatty
coconut oil is pumped to a homogenizer and is
there contacted with 96 c. 0. per minute of an
hydrous ethyl alcohol containing 0.7 5% of sodium
hydroxide. The materials are thoroughly mixed
acids.
Ea‘ample IV
About 100 parts by weight of coconut oil are
charged into a stainless steel bomb with 72 parts
of methyl alcohol and 1 part of concentrated sul
phuric acid. The bomb is brought to a tempera
mately ten minutes. The coil is jacketed with
ture of 135° C. and maintained at approximately
low pressure steam at a temperature of about
that temperature for some forty-?ve minutes
100° C. and is equipped with means for maintain‘
with intermittent shaking. It is then cooled to
ing a back pressure upon the contents thereof. 45 about 25° C., and its contents are washed with
The reaction mixture is kept under a pressure
water, dried and ?ltered. Theyield of distillable‘
in the homogenizer, and the mixture is run into
a reaction coil having a holding time of approxi
of about 90 pounds per square inch absolute and
is run from the reaction coil at a temperature of
about 100° C. The mixture is passed with reduc
‘ material obtained, comprising methyl esters of
the coconut oil fatty acids, is about 97.3% of the
calculated theoretical yield.
tion in pressure through a preheater, which is 50
Example V
also steam jacketed, and the temperature of the
mixture is there raised to 110° C. The ethyl al
Employing the same equipment and procedure
cohol is vaporized within the preheater pipe, and
as in Example IV, 285 parts by weight of No. 4
the liquid-vapor mixture is run into a packed
tallow containing about 14% of free fatty acids
column for separation of the vapor. A series of 55 are charged into a bomb with 160 parts of methyl
steam coils is located at the bottom of the column
alcohol and about 3 parts of concentrated sul
and serves as a reboiler. The ethyl alcohol is
phuric acid. After forty-?ve minutes at a tem
removed at the top of the column to- a condenser
perature of about 135° C. and removal of excess
and receivers, and the ethyl esters of coconut oil
alcohol, a yield approximately 96.4% of the cal
acids, glycerine and any soap present drop 60 culated theoretical is obtained.
through the series of steam coils into a settling
Example VI
chamber. Glycerine separates out in the lower
A
substantially
anhydrous
mixture of coconut
layer, which is withdrawn, and theupper layer.
oil and ethyl alcohol in approximately equal parts
comprising the ethyl esters is removed for puri
?cation and further processing.
65 by weight is heated to about 130° C. under su?i
cient pressure to keep the alcohol in the liquid
Example II
phase. The mixture is passed into a stainless
About 285. parts by weight per minute of sub
steel homogenizer at a rate of about 200 parts by
stantially anhydrous cottonseed oil is mixed with
weight per minute and is contacted there with
160 parts per minute of substantially anhydrous 70 about 1' part per minute of concentrated sul
methanol and 1.6 parts per minute of sodium hy
phuric acid, meanwhile maintaining the pres
droxide (about 0.04 mol of sodium hydroxide per
sure. The materials are thoroughly mixed at
equivalent of oil) during a period of 4.1 minutes. ' 140° C. for about four minutes, and the e?iuent
After thorough mixing, the materials are
into
is run into a steam-jacketed reaction coil having
a reaction coil, where they are heated to between 75 a holding time of approximately ?ve minutes.
4
2,383,579
The temperature is kept at about 140° C. and a
back pressure of 165 pounds per square inch as
solute is maintained within the coil. The reac
tion mixture is ?ashed into a vaporization cham
ber maintained at 135° C.,' and excess ethyl al
cohol is volatilized and removed. The remainder
of the mixture is passed into, a settling tank,
from which glycerine and ethyl esters are sepa
ume per minute. The oil mixture and the alcohol
run through the pump together and are mixed
therein during a period of about six seconds.
The alcohol contains about 0.75% anhydrous
caustic soda based on the oil used. The reaction
mixture in the coil is heated to about 123° C. and
is under a gauge pressure therein of about 125
pounds per square inch. The coil has a holding
rately withdrawn.
time of about thirty-seven seconds at the present
10 throughput rate, and at the end of this period
Example VII
the eiliuent at about 123° C. is ?ashed into a
About 215 parts by weight per minute of coco
vaporization chamber maintained at about 129°
nut oil are run into a homogenizer and are there
C. and atmospheric pressure. The excess meth
mixed with about 230 parts per minute of ethyl
anol is volatilized, and the residue is passed to
alcohol containing about 0.6% of sodium hy
an acidi?cation and settling tank, where it is
droxide. The materials are thoroughly mixed
acidi?ed, washed, dried and distilled. A yield of
for about three minutes, and the mixture is run
esters equivalent to about 97.5% of the calculated
into a heated reaction coil of such dimensions as
theoretical yield is obtained.
to be able to contain 3,200 parts of material, that
Example X
is, having a holding time of about seven minutes
at the present rate of feed. The materials are
A substantially anhydrous mixture of coconut
heated therein to about 100° C. and are main
oil and tallow in the proportion of about 1 to 4
tained under a back pressure of about 90 pounds
is heated to about 75° C. and run at about 785
per square inch absolute. The'e?iuent from the
parts by volume per minute directly into a reac
reaction coil is run. into a preheater at substan- .
tion coil having a capacity of about 785 parts by
tially atmospheric pressure and it is there heated
volume. Substantially anhydrous methyl alcohol
to about 110° C. Unreacted ethyl alcohol is va
containing about 0.75% anhydrous caustic soda
porized, and the liquid-vapor mixture is passed
on the basis of oil used is also run directly into
to a packed column which is situated over a series
the coil at a rate of about 500 parts by volume
of steam coils. The steam coils serve as a re 30 per minute. The reactants mix in the coil and v
boiler, and steam is furnished to them at a pres
are heated to about 123° C. under a pressure of
sure su?icient to provide an outside surface tem
125 pounds per square inch gauge during the
perature of about 130° C. vaporized unreacted
period of 0.61 minute when they are passing
alcohol is withdrawn at the top of the column
therethrough. The e?iuent passes through a so
and is condensed and stored for reuse in the
lution heater at atmospheric pressure and is
process. The residue ?ows through the reboiler
vaporized in a ?ash chamber at 115° C. Excess
and into ar acidi?cation tank, where su?icient
methyl alcohol is volatilized, and the ‘residue is
sulphuric acid is added to provide an acidic re
treated as in Example IX, a yield of esters equiv
action mixture having a pH of about 4.0. The
alent to about 97.5% of the calculated theoretical
acidi?ed mixture is then settled, and a lower 40 yield being recovered.
glycerine layer is removed. The upper layer
comprising the ethyl esters of coconut oil acids
over?ows through an outlet in the upper portion
of the settling tank.
and coconut oil in'the ratio of 4 to 1 is heated
‘
Example VIII
About 285 parts by weight per minute of cot
tonseed oil are thoroughly mixed with about 160
parts per minute of methyl alcohol and about
1.6 parts per minute of sodium hydroxide for a
period of about thirty seconds, the reactants be
ing at about 25° C. throughout. The mixture
is then run into a reaction coil having a holding
time of about thirty seconds and the tempera
ture is raised to about 130° C.
Example XI
A substantially anhydrous mixture of tallow
Suiilcient pres
sure is maintained within the coil to keep methyl
alcohol in the liquid state. The e?iuent from the
coil is ?ashed into a vaporization chamber at
> to 113° C. and run to the inlet of a .pump at a
rate of about 785 parts by volume per minute.
Substantially anhydrous methanol containing
0.75% dry sodium_hydroxide on an oil basis is
heated under pressure to about 119° C‘. and run
to the same pump inlet at about 500 parts per
minute. The capacity of the pump is such that
the reactants pass through at these rates in about
six seconds. The materials are pumped into a
reaction coil, through which they pass in about
seventy-eight seconds, and the temperature of
the reaction mixture is raised to about 138° C.
under a gauge pressure of about 163 pounds per
square inch. The ef?uent from the coil passes
atmospheric pressure and then into a second ‘ into a tube under atmospheric .pressure, where
chamber under a vacuum of about 26 inches of 60 the temperature is reduced to about 133° C., and
mercury, and excess methanol is volatilized and
it is then treated in an atmospheric vaporization
withdrawn. The residue flows into a settling
chamber at about 129° C., where excess alcohol
tank, where a lower glycerine-containing layer is
is volatilized. The residue is treated as in Exam
withdrawn. The upper layer is removed, washed,
dried, and vacuum distilled, and a yield of methyl
esters of cottonseed oil equivalent to about 97.0%
of the calculated theoretical yield is obtained.
Example IX
A dry mixture of about 80% tallow to about
20% coconut oil is preheated to about 73° C. and
is pumped into a reaction coil at a rate of about
785 parts by volume per minute. Substantially
anhydrous methanol at about 22° C. is pumped
into the coil at a rate of about 500 parts by vol
ple IX, and a yield of esters equivalent to about
98% of the calculated theoretical yield is obtained.
Example XII
Referring to the ?gure, a mixture of about 20%
of coconut oil and 80% of tallow is drawn from a
calibrated supply tank through a salt ?lter to
remove moisture therefrom and is pumped into
a mixing chamber. Solid substantially anhydrous
caustic soda is dissolved in substantially anhy
drous methyl alcohol in the proportion of 0.17
part by weight of caustic to 10.4 parts of meth
5
2,388,679‘
anol, and the alcoholic solution is also pumped
from the principles and true ‘spirit ,of the in
from a supply tank to the mixing chamber. The ~
vention.
fatty oil mixture is pumped to the- chamber at
the rate of 22.3 pounds per hour, and the alkaline -
alcohol is pumped into the chamber in con?uence
therewith at the rate of 10.57 pounds per hour.
The mixing chamber is equipped with' twenty
motor-driven impeller blades adapted to run at
800 R. P. M., and the temperature of the, mixing
We claim:
'
-
.
' 1. The process which comprises heating a fatty
acid ester of an aliphatic polyhydric alcohol with
an aliphatic monohydric alcohol having one to
about six carbon atoms per molecule in the pres
ence of an alcoholysis catalyst at a temperature
above the normal ‘boiling point of said aliphatic
chamber is 40° C. Under these conditions in the 10 monohydric alcohol and at a pressure sufficient
mixing chamber, the two-phase system reaches
a ?nely-divided state and the reaction is initiated.
The volume of the mixing chamber is such
to maintain the monohydric alcohol in liquid
phase, thereby providing a liquid body contain
ing alkyl esters and polyhydric alcohol; and re
covering the alkyl esters and the polyhydric
that its‘ holding time is about four minutes, and
the e?iuent passes into a reaction coil which 15
2. The process which comprises heating a fatty
comprises a series bank of double pipe units,
glyceride, with a monohydric alcohol having one
the volume of which is equivalent to about ten
to about six carbon atoms per molecule in the
minutes’ reaction time. Low pressure steam is
presence of an alcoholysis catalyst at a tempera
supplied to the outer pipe, which forms an an
ture above the normal boiling point of said alco
nular jacket ‘for the reaction coil, and a reaction 20 hol and at a, pressure suf?cient to maintain a
temperature of about 100° C. is thereby main
substantial proportion of said alcohol in a liquid
tained. The coil outlet is furnished with a pres
phase, thereby providing a liquid body contain
sure controller which maintains a gauge pressure
ing monohydric alcohol esters and glycerine; and
of about '75 pounds per square inch within the
separately recovering said esters and glycerine.
coil. Under these conditions of temperature and 25 3. A process for treating fatty materials which
pressure, the alcohol is substantially unvolatil
comprises heating a fatty glyceride with a satu-'
'ized, and a high yield of methyl esters and glyc
' rated, aliphatic, monohydric alcohol having one
erine is obtained within the reaction time and
to about six carbon atoms per molecule in the
with the simultaneous conversion of substantially 80 presence of an alcoholysis catalyst at a tempera
all of the catalyst to soap.
ture about 80° C. to about 160° C. but above the
The reaction mixture ?owing from the coil is
normal boiling point of the alcohol and at a
released to substantially atmospheric pressure
pressure substantially above the vapor pressure
within a steam-heated tubular preheater, in
of said alcohol at the temperature employed,
which the latent heat of vaporization of steam 35 thereby providinga liquid body containing alkyl
is added to the vaporizing unreacted alcohol at
esters and glycerine; and recovering alkyl esters
about 100° C. The liquid-vapor mixture is passed
and glycerine from said liquid body.
alcohol.
to a steam-heated separation or ?ash chamber
-
‘
4. The process as set forth in claim 3 wherein
at substantially atmospheric pressure. The va
' the alcohol employed is methyl alcohol and
porized alcohol is withdrawn and is condensed 40 wherein the alkyl esters produced are methyl
in a tubular condenser as substantially anhydrous
alcohol for reuse. The residue after vaporiza
tion of the alcohol flows into a settling tank,
where it is cooled to about 52° C. and is acidi?ed
with dilute sulphuric acid. The acidi?ed mix
ture is allowed to stand, and two layers are ob
esters.
5. The process as set forth in claim 3 wherein
the alcohol employed is ethyl alcohol and where
in the alkyl esters produced are ethyl esters.
6. A process for treating fatty materials which
comprises heating a fatty glyceride with an ex
cess of a saturated, aliphatic, monohydric alco
The lower layer, comprising glycerine together
hol having one to about‘ six carbon atoms per
molecule, said ‘excess being about three to about
with the water and salt resulting from acidi?ca
tion of the mixture, is withdrawn. The upper 50 ?ve times the stoichiometric amount of said alco
tained.
hol required fOr alcoholysis of said glyceride, in
layer, comprising the methyl esters of the tallow
the presence of an alcoholysis catalyst in the pro
and coconut oil fatty acids, the fatty acids made
portion of about 0.3 mol to about .10 mol of
by acid splitting of the soap formed by saponi?
said catalyst per equivalent of glyceride, at a
cation of the esters with the caustic catalyst,
and partially reacted mono- and, di-glycerides, 55 temperature of about 80° C. to about 160° C. but
above the normal boiling point of the alcohol
is also removed. This operation gives about 98%
and at a pressure substantially above the vapor
conversion of available fatty acid to methyl
pressure of said alcohol at the temperature em
esters and about 94% liberation of the available
ployed, thereby providing a liquid body contain
glycerine, based upon the calculated theoretical
yields.
_
60 ing alkyl esters, glycerine and unreacted alcohol;
removing unreacted alcohol therefrom; and sep
The ester fractions obtained according to the
arately recovering alkyl esters and glycerine,
present invention, with or without washing
7. A process for treating fatty materials which
and/or subsequent puri?cation, can be employed
comprises mixing a fatty glyceride with a sat
in many chemical processes and products, as in
the paint, perfumery, lubricating oils, medicinals 65 urated, straight-chain, monohydric alcohol hav
and other ?elds. They may be used for chemical
reductions and in many chemical syntheses and
ing one to about six carbon atoms per molecule
and with an alcoholysis catalyst; heating the
one of their greatest outlets for volume con
mixture at a temperature of about 80° C. to
sumption is in the soap-making industry.
Although the present invention has been de
about 160° C. but above the normal boiling point I
scribed with reference to particular embodiments
and examples, it will be apparent to those skilled
in the art that variations and modi?cations of
this invention can be made and that equivalents
can be substituted therefor without departing
70 of the alcohol and at a pressure substantially
above the vapor pressure of said alcohol at the
temperature employed, thereby providing a liquid
body containing alkyl esters and glycerine; and
recovering alkyl esters and glycerine from said
liquid body.
- 6
2,388,579
8. A process for treating fatty materials which
comprises establishing a liquid pool containing
a fatty glyceride, a saturated, straight-chain,
cohol therefrom; and recovering ethyl esters and
glycerlne from said liquid body.
monohydric alcohol having one to about six car
bon atoms per molecule, alkyl esters, glycerine
and partially reacted glycerides; continuously in
troducing a fatty glyceride and a saturated,
straight-chain, monohydric alcohol having one to
about six carbon atoms per molecule together
with an alcoholysis catalyst into said liquid pool;
continuously withdrawing a. portion of said liquid
pool; regulating the rates ofsaid introduction
and said withdrawal with respect to the size of
the liquid pool to keep the fatty glyceride and
presence of an acidic alcoholysis catalyst‘for up
to about thirty minutes at a temperature above
the normal boiling point of said alcohol and at
a pressure substantially above the vapor pressure
of said alcohol at the temperature employed,
thereby providing a liquid body containing alkyl
esters and glycerine; and recovering alkyl esters
and glycerine from said liquid body.
14. A process for treating fatty materials which
the alcohol in contact in the pool in the presence
of the alcoholysis catalyst for a period of time
comprises heating a fatty glyceride with an excess
of a saturated, straight-chain, monohydric alco
hol having one to about six carbon atoms per
sumcient to provide thorough mixing and insuffi
cient for the reaction to go to completion; heat
ing the withdrawn portion at a temperature
above the normal boiling point of the alcohol
molecule in the presence of an acid alcoholysis
catalyst for up to about thirty minutes at a tem
perature of about 80° C. to about 160° C. but above
and at a pressure substantially above the vapor
_ pressure of said alcohol at the temperature em
the normal boiling point of the alcohol and at a
pressure substantially above the vapor pressure of
ployed, thereby providing a liquid body contain
ing alkyl esters and glycerine; and recovering
alkyl esters and glycerine from said liquid body.
9. A process for treating fatty materials which
said alcohol at the temperature employed, there
by providing a liquid body containing alkyl esters,
glycerine and‘unreacted alcohol; volatilizing un
comprises heating a fatty glyceride with a satu
reacted alcohol from said liquid body at a tem
perature below the temperature of substantial re
versal of the reaction upon removal of the alco
rated, aliphatic, monohydric alcohol having one
to about six carbon atoms per molecule in the
presence of an alkaline alcoholysis catalyst for
up to about ten minutes at a temperature above
the normal boiling point of said alcohol and at
a pressure substantially above the vapor pressure
,
13. A process for treating fatty materials which
comprises heating a fatty glyceride with a satu
rated, aliphatic. monohydric alcohol having one
to about six carbon atoms per molecule in the
a
hol; and recovering alkyl esters and glycerine,
from said liquid body.
15. A process for treating fatty'materials which
comprises heating a fatty glyceride with an excess
of methyl alcohol in the presence of an acid alco
35 holysis catalyst at a temperature of about 90° C.
esters and glycerine; and recovering alkyl esters
to about 130° C. and at a pressure substantially
and glycerine from said liquid body. _
above the vapor pressure of methyl alcohol at the
10. A process for treating fatty materials which
temperature employed, thereby providing a liquid
comprises heating a fatty glyceride with an ex
body containing methyl esters, glycerine and un
cess of a saturated, straight-chain, monohydric 40 reacted methyl alcohol; removing unreacted
alcohol having one to about six carbon atoms per
methyl alcohol therefrom; and recovering methyl
molecule in the presence of an alkaline alcoholy
esters and glycerine from said liquid body._
sis catalyst for up to about ten minutes at a tem
16. A process for treating fatty materials which
perature of about 80° C. to about 160° C.'but above
comprises heating a fatty glyceride with an ex~
the normal boiling point of the alcohol and at a 45 cess of ethyl alcohol in the presence of an acid
pressure substantially above the vapor pressure
alcoholysis catalyst at a temperature of about 90°
of said alcohol at the temperature employed,
C. to about 130° C. and at a pressure substantially
thereby providing a liquid body containing alkyl
above the vapor pressure of ethyl alcohol at the
of said alcohol at the temperature employed,
thereby providing a liquid body containing alkyl
esters, glycerine and unreacted alcohol; volatiliz
temperature employed, thereby providing a liquid
ing unreacted alcohol from said liquid body ‘at a 50 body containing ethyl esters, glycerine and unre
temperature below the temperature of substan
acted ethyl alcohol; removing unreacted ethyl al
tial reversal of the reaction upon removal of the
cohol
therefrom; and recovering ethyl esters and
alcohol; and recovering alkyl esters and glycerine
glycerine from said liquid body.
from said liquid body.
.
‘.17. The‘ process which comprises bringing a
11. A process for treating fatty materials which 55 stream of fatty material from the class consisting
comprises heating a fatty glyceride with an ex
of fats and oils into con?uence with a stream of
cess of methyl alcohol in the presence of an al
lower aliphatic monohydric alcohol in the pres
kaline alcoholysis catalyst at a temperature of
ence of an alcoholysis catalyst and under turbu
about 90° C. to about 130° C. and at a pressure
lent conditions, subjecting the mixture ‘to a tem
substantially above the vapor pressure of methyl 60 perature
above the normal boiling point of said
alcohol at the temperature employed, thereby
alcohol and at a pressure su?icient to maintain.
providing a liquid body containing methyl esters,
the alcohol in liquid phase whereby alcoholysis of
glycerine and unreacted methyl alcohol; remov
fatty material takes place, introducing the reac
ing unreacted methyl alcohol therefrom; and re
tion mixture into a zone of lower pressure to vola
covering methyl esters and glycerine from said 65 tilize
unreacted alcohol therefrom and leave a
liquid body.
residue containing glycerine and alkyl esters, and
12. A process for treating fatty materials which
thereafter separately recovering glycerine and al
comprises heating a fatty glyceride with an ex
cess of ethyl alcohol in the presence of an alkaline
kyl esters from said residue.
'
18. The continuous alcoholysis process which
alcoholysis catalyst at a temperature of about 90° 70 comprises continuously bringing a stream of fatty
C. to about 130° C. and at a pressure substantially
material from the class consisting of fats and oils
‘above the vapor pressure of ethyl alcohol at the I into con?uence with a stream of lower aliphatic
temperature employed, thereby providing a liquid
monohydric alcohol in the presence of an alco
body containing ethyl esters, glycerine and unre
holysis catalyst and under turbulent conditions.
acted ethyl alcohol; removing unreacted ethyl al 75 subjecting
the mixture to a temperature above
2,383,579
the normal boiling point of said alcohol and at a
pressure sumcient to maintain the alcohol in
7
continuously withdrawing the volatilized alcohol
from said zone, continuously withdrawing the res
idue from said zone, and separately recovering
glycerine and alkyl esters from said withdrawn
reaction mixture into a zone of lower pressure to 5 residue.
liquid phase whereby alcoholysis of the fatty ma
terial takes place, continuously introducing the
volatilize unreacted alcohol therefrom and leave
HAROLD DWAINE ALLEN.
a residue containing glycerine and alkyl esters,
WILLIAM ASHLEY KLINE.
Certi?cate of Correction
Patent No. 2,383,;579
August 28, 1945
HAROLD DWAINE ALLEN ET AL.
'
It is hereby certi?ed that error appears in the printed speci?cation of the
above numbered patent requiring correction as follows:
‘
Page 5, second column, line 53, for “about 0.3 mol” read about .03 11ml;-v
same may conform to the record of the case in the Patent O?ice.
Signed and sealed this 6th day of February, A. ‘D. 1951.
[we]
THOMAS F. MURPHY,
Assistant Oommz'ssz'oner of Patents.
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