- March 22, 1932.

H, M, sumo-r

1,850,836

PROCESS FOR THE MANUFACTURE OF ACETAL

Filed Dec. 29. 1927

a/thyvuws ,

! 1,850,836

Patented Mar. 22,, 1932

1 UNITED STATES PATENT

oFI-ucu

HENRI marm/ comer, or mun. rnsncn, assrenoniro socmrn mourns nus

, nrsrrnnnnrns nns nnuxrsnvnns, or manna, nntrx-snvnns, FRANCE

PBOGESS FOR THE MAN'QTAQTURE OF AGETAL

I Application ?led December 29, 1927, Serial No. 243,386, and in vBelgium January 3, 1927. _

The preparation of di-ethylic acetal by the a de?nite result, the output of pure acetal is
use of ordinary alcohol and of acetaldehyde,

only 65 per cent.

The second method consists in adding to the

or its polymers, has already been consid
ered in various scienti?c papers, but the op . mixtures in the reaction, liquids which are in
soluble in water, such as gasoline. This causes
5 erating methods proposed have not o?ered the separation of an aqueousilayer' and a
altogethersatisfactory results.
.

The operation is usually performed as fol

lows :-.

layerrich in acetal. The latter is puri?ed '

by washin and rectifying. In this method,

Alcohol and aldehyde are placed together, the yield 0 _ acetal is increased, but it is neces-
reaction being produced by means of a sary to proceed with laborious recovery oper- '
1,0 the
certain quantity of a catalyst, such as hydro ations by distillation, in order to attain the
' chloric, sulphuric, toluene sulphonic, or.ace

90 per cent yield speci?ed by the author.

I have devised the improved process, the"

tic acids, hydrogen phosphide, calcium chlo- subject-matter
of the present invention. The
' ride, various metallic salts, or the like.
said
process
comprises
the following features;
Acetal
is
formed,
and
the
production
stops
15
at the state of equilibrium: Alcoho1+ acetal- > > 1. The use of a quantity of acid to start

dehyde <1 acetal+water ; so that the reaction the reactiomwhich is only from % toil,
medium contains the four prdductsu The of that generally used in ordinary practice;
acetal has a boiling point of-1042 degrees C. this- small quantity su?ices to cause the pro-4
which is much higher than'that of the other , duction of acetal, and it has further the
liquid constituents used, so_ that it would advantageous result'of reducing to a min

appear to be an easy. matter to separate it imum' the quantity of salt'formed after the '
' from these latter by distillation, for the said acid has been neutralized. Otherwise stated,
substances would be distilled over, while the and as. clearly appears from the example

. _

acetal would remain. Unfortunately, acetal given below, the quantityof acid used is .75
approximately equal to 0.03 percent of the
forms in the ?rst'place with alcohol alone, quantity
(by weight) of the materials used.
I ~and in the second place with alcohol and
acid .is neutralized by a weak alkali
water, azeotropic mixtures, rich in acetal, or- 2.byThe
a reagent adapted to produce an alka- ,
whose boiling points are below 78.3 degrees,
line
reaction
until the 'obtainment of a very 80
and
hence
during
the
distillation
the
major
so
slight
alkaline
e?ect with bromothymol blue;
part of the acetal will be brought vover in
all
acidity
which
might cause the decomposi
these mixtures, and at the end of the dis
tion
of
the
acetal
during the distillation, and
tillation, but a small amount, in the pure state, all alkalinity greater
than that above indi- '
8.5. To obviate this difficulty, two principal cated which might'cause the resini?cation of

25

will remain.

>

'

'

'

the substances, must be avoided.

3. The continuous separation of the pure
One oi these consists in the useiof certain acetal
b distillation. in three stages.
salts, such as calcium chloride, to absorb the
The st stage consists in removing, 'by
water which is formed (in this case it has al distillation, the. whole of the acetaldehyde
ready served as a catalyst for the reaction).
and also a part of the alcohol, leaving as
[This results inthe formation of a layer aresidue the acetal, the water and the re
which has been made rich in acetal, which is mainder of the alcohol ;'the second stage con
puri?ed by washing with water, drying by sists in the removal of this residue of wa
.45 calcium chloride, and rectifying. However, ter and alcohol by distillation, by the use as
this method of proceeding has a disadvan of an auxiliary liquid insoluble in water,;
tage, infthat'it leads to the formation of which forms with the water and alcohola

methods have been hitherto proposed.

mixture having a minimum boiling point,

proportions-of all the substances used, and" leaving pure acetal asa residue of this dis-l

_ aqueous solutions containing greater or less

50

this will much complicate the treatment. I As tillation; the third stage consists in recover in
/

1,850,836 1

ing from the resulting mixture having the of the surface heating there will beproduced
minimum boiling point the auxiliary liquid, an azeotropic mixture of benzine, alcohol and
by washing, and the alcohol, by distillation, water which .is then condensed in the con
and in causing them to enter the cycle of denser 12; a certain part-of said mixture pro

operations.

70

ceeds back through the pipe 13, and there

The following example of the said process mainder circulates through the pipe 14 into

with reference to the appended drawing, the lower part of the scrubber 15. The acetal
shows the principles of the said invention.
descends to the bottom of the apparatus; 10
To the vessel 1 is supplied~cooling effec land is discharged thence through the pipe 16; .
10 tively by means of the worm 292' kgs. of it is cooled in the cooling device 17_. The 75
alcohol at 100 degrees C. and 45 kgs. of condensed azeotropic mixture which enters
acetaldehyde, to which is added 45 grams the lower part of the scrubber 15, receives, by
(that is to say the Km of the weight of the contrary ?ow, a slight amount .of. Water
acetic aldehyde in use) of gaseous HCl in the through the pipe 18. The benzine settles, and
15 form of acid at 22 degrees B. After 2 hours it enters the distilling apparatus 10 throu h 80
of contact, the reaction is complete, and the the ipe 19. The liquid issuing from t e
mixture contains acetal. The mass is care scrugber through the pipe 20 consists of water
fully neutralized by adding the proper quan and alcohol; it enters the distilling appara

25

tity of sodiumbicarbonate, until the solu tus 21, in which the alcohol is concentrated
tion becomes slightly alkaline as shown by to 96 degress in the known manner, and then 86
bromothymol blue. The liquid thus neutral ?ows through the pipe 22 into the vessel 23. .
ized is emptied into a recipient 3, and the The residual water issues through the pipe 24.
The aldehyde, mixed with a small'amount
same operation is repeated in the vessel 1,
so as to constantly supply the said recipient of alcohol, which is collected from the vessel
which is used for the feeding of the con~ 8, and the alcohol which is collected from the
tinuous distillation system.
vessel 23, will serve again for the reaction in

The upright distilling apparatus 4, pro

80

the vessel 1.

- '

90

vided with surface heating, is regularly sup? ' In this process, the yield is total, which
plied with the liquid from the recipient 3 means that the products which havenot re
through the pipe 5. The heating and the acted are entirely recuperated and sent back

95

back action are so'regulated that the whole into the apparatus together with the amounts of the acetaldehydeand if necessary apart of fresh products, so-that there is no loss.
ofthe alcoholwill be brought over by the Thus I obtain in the form of acetal, the whole
distillation. The vapours of these liquids of the products used in the reaction.
Obviously, modi?cations can be made in 100,
condense in, the, condenser 6; a portion cir
culates back through the pipe 7, and the re the rocess herein speci?ed'without depart
mainder ?ows 'into the receptacle 8. There ing' rom the principle of the invention.
What I claim is :
p

'
will descend to the lower part of the appa
1. Process for the manufacture of di
ratus 4 a mixture of acetal, alcohol and wa
40 ter. By the use of a suitable heating, the ethylic acetal from ethylic alcohol and acetic 105
said mixture is vaporized, and the mixture aldehyde including the use of one of the
of vapours thus produced cannot ascend col known acids usually employed as catal sts
umn 4: because it is driven back b the prod-' for that purpose, characterized by the act

uots ?owingback from tube 7 (yand which vthat the condensation of the acetic aldehyde

5 consist chie?y of acetaldehyde, a very vola

tile product) to the lower part of the column.
Now in the lowerpart of any distillation
" column there is a pressure which .is approxi

and the alcohol is. effected by the use of'a no

quantit of the acid usedas catalyst which

is equa to about 0.03 percent -by- weight of
the materials used.

mately equal to the sum of the heights of . 2. Process for the manufacture- of di
the liquids on the plates. The vapours of; ethylicfacetal from ethylic alcohol and acetic
'acetal, alcohol and water formed in the-lower, aldehyde, characterized by the fact that the

part ofacolumn 4 therefore issue preferably" condensation of the acetic aldehyde and the
through tube 9 and enter the intermediate alcohol is e?'ectedb ' the. use as catalyst of
part of column 10, where the pressure is a quantity of hydroc loric acid equal-to about
65 about one half .of that in the lower'part of 0.03 percent by weight of the materials used.
column 4. The salt contained in the liquid,-v

116

p '
120

3. Process for the manufacture of .di- -'

ethylic acetal from ethylic alcohol and acetic

kgs. of acetal obtained-will be precipitated aldehyde includingihe use of one of the
and is collected in a vessel 11 in the usual known acids usually employed as catalysts
for 'that'purpose, characterized by the fact
In the apparatus 10 is preliminaril placed ~v that the condensation of the acetic aldehyde
a certain quantity of benzine whic serves and the alcohol is effected by the use of a

' some 85 grams of sodium chloride per 100

manner.

'

- as an auxiliary li uid so that the'said liquid quantity of the acid used as catalyst which

will be distribu
on about % of the upper .is equal to about 0.03 percent by weight of
'5 part of the said apparatus. . Under the e?ect the materials used and in that the resulting

125

1,850,888

due with an auxiliary liquid insoluble in wa

which forms with the water and the alco
of the reaction is attained, by a ding the ter
hol a mixture having a minimum boiling
strictly necessary amount of a weak alkali.
point, in such manner as to obtain on the one
4. A process for the manufacture of _di- ' and the separated; acetal at the bottom 0
ethylic acetal, which consists in condensing the distilling apparatus and on the other hand
acetic aldehyde and alcohol in the presence the said mixture having a minimum boiling
of one of the known acids usually employed proint, in washing this mixture discharged
as catalysts for that purpose, in separating, om the distilling apparatus with water in
by continuous distillation, from the products order
to remove the auxiliary liquid, in sub
10 formed by the reaction, the acetic aldehyde jectingthe water and the alcohol to athird
and a part of the alcohol which has notre
in order to separate them from
acted, so as to obtain as a residue, the acetal, distillation
one another, and in' causing the alcohol to
_ the water, and the remainder of the alcohol, enter the cycle of operations. 7
I
in distilling these latter products with an
In testimony whereof I have signed this

solution is neutralized, when the eqiuilibrium

75

80

auxiliary liquid insoluble in waterand form

15

ing with the water and alcohol a mixture

speci?cation.

'

HENRI MARTIN GUINOT.

having a minimum boiling point, in such

manner as to obtain the acetal as a residue, '

in washing the said mixture having the 1111111

mum boiling point which issues from the sec

20

85

ond distillation in'such manner as to remove

the auxiliary liquid, and in subjecting the

alcohol and water to a third distillation in
25

order to eliminate the water, and in causing

the alcohol to enter the cycle of operations.
5. A process for the manufacture of di

90

of one of the known acids usually employed

as, catalysts for that purpose, in neutralizing

95

ethylic acetal, which consists in condensing

acetic aldehyde and alcohol in the presence

30

the resulting solution when the equilibrium

of the reaction is obtained, in distilling the
products of the reaction in such manner as to

ioo

separate on'the one hand the .acetic aldehyde

36 and a part of the alcohol which hasnot re- ' i

' acted, and to obtain on the other hand the

acetal, the water, and the remainder of the

alcohol, in again distilling these last-men
tioned products .with an auxiliary liquid
40

105

which is insoluble in water and which forms

with the water and alcohol a mixture having
a minimum boiling point in such manner as
to obtain on the one hand the acetal and on
the other hand the said mixture having the i

45

minimum boiling point, in washin the said

mixture to recover'the auxiliary ' quid, in

distilling the remaining mixture of alcohol

and water 'to remove the water, and in causmg ,

l the alcohol to enter the cycle ofv operations.

5 6. A process for the manufacture of di

115

ethylic metal, which consists 'in condensing

acetic aldehyde and alcohol by means of a,

quantity of hydrochloric acid eqpal to 0.001

of the weight of the acetic alde yde in use,

120

55 in neutralizing the resulting solution, when

the egmlibrium of the reactionhas-been ob-
taine , by adding the quantity of sodium
the
bicarbonate
products strict
of theyreaction
necessary,
so asinto separate
.

60 on t 0 one hand the acetaldehyde' and a

g -

rt

>125

of the alcohol which has not reacted, an on

the other hand to obtain as a residue

acetal, the water and the remainder of the

alcohol in causing the acetaldehyde to enter

65 the cycle of operations, in distilling the red-

130'