July 19, 1955 L.

ALHERITIERE ET AL 2,713,598
PROCESS FOR MAKING ACETALDOL FROM ACETALDEHYDE
Filed April 5, 1950
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Louis fNVENTORS,
AlheriterE,
Georeges Go Breon.
" Aal? 4-24, 42-e
742, ATTORNEY.5,
 United States Patent Office 2,713,598
Patented July 19, 1955
2
2,713,598 System to
ing water. take care of Summer temperatures of the cool
PROCESS FOR MAKING ACETALDOL FROM The principal object of the present invention is to avoid
ACETALDEHYDE
Louis Alhéritière and Georges Gobron, Melle, France, as at least some of the above-mentioned difficulties and pro
signors to Les Usines de Melle (Societe Anonyme), vide a simple process for the production of acetaldol of
Saint-Leger-les-Melle, high purity. Another object is to provide a two-stage
Republic of France France, a corporation of the condensation process whereby acetaldehyde can be con
densed into acetaldol rapidly and economically. Still an
Application April 5, 1950, Serial No. 154,021 othersuch
out
0. object is to provide a simple apparatus for varying
process.
Claims priority, application France May 23, 1949 The invention accordingly comprises the novel proc
7 Claims. (CI. 260-602) esses and steps of processes, specific embodiments of
which are described herein by way of example only and
This invention relates to the production of acetaldol. 5 to in practice
accordance with the manner in which we now prefer
the invention.
Acetaldol is ordinarily produced by condensing acetal
dehyde by means of a catalyst. The main difficulty in We have found in accordance with our invention that
condensing acetaldehyde into acetaldol is that of remov we may carry out a continuous process for producing
ing the heat which is rapidly and abundantly evolved by acetaldol comprising continuously flowing a liquid mix
the reaction and avoiding the secondary reactions which 20 ture of acetaldehyde, acetaldol and aldolization catalyst,
yield resinous by-products such as polyaldols. Such as an aqueous solution of sodium hydroxide, through
In the United States Patent No. 2,489,608, of which two Zones under controlled conditions of temperature,
one of the present applicants is the inventor, a process is time and pressure. In the first zone which includes an
described in which the formation of acetaldol takes place elongated path of restricted cross-sectional area, there is
while the reaction mixture is boiling. The heat evolved 25 caused a continuous flow at a temperature somewhat
by the reaction is absorbed by vaporization of the acetal above 40 C., preferably about 45 C., at a pressure to
dehyde in the mixture. This process is conducted pref prevent boiling at such temperature for a period of not
erably in a plate still provided with bubble caps and there over one minute to cause aldolization to begin. We then
is no water-jacketing of that part of the system where the continuously pass the so-treated liquid through a second
acetaldehyde is transformed into acetaldol. The heat 30 Zone which includes an elongated path of restricted cross
is absorbed, as stated, by the vapors passing off from the sectional area at a temperature materially below 40 C.,
boiling mixture. Under normal conditions, as stated in preferably in the range of about 20° C. to about 35° C.,
the patent, the conversion in accordance with the said preferably for less than about 5 minutes to cause aldoli
patent is 35% to 15% of the acetaldehyde to acetaldol. zation to proceed. The pressure is preferably produced
It has also been proposed to effect the condensation of 35 by arranging the second Zone above the first zone, the
acetaldehyde by a two-stage process. Such a process has liquid in the two zones being continuous throughout the
been described in French Patent No. 942,081. Accord two Zones, the second Zone terminating at a height so
ing to this French patent, an acetaldehyde-acetaldol mix that the desired pressure in the first zone is developed
ture is circulated at high speed through a cycle including a as a hydrostatic pressure. We have also found in accord
reaction vessel and a cooling device. This mixture is fed ance with our invention that a simple apparatus may be
continuously with acetaldehyde and an aqueous solution 40 employed in which a conduit constituting a first zone of
of condensing agent, and a quantity of liquid equal to the 8', aldolization is employed and directly connected thereto is
total feed is continuously withdrawn from this mixture a second conduit constituting a second aldolization zone
and sent into a cooled Zone, in which condensation is for continuing aldolization of material received from the
completed up to the desired extent and then stopped by first conduit. In this apparatus, the second aldolization
the addition of acid. In this process, the circulating mix Zone extends above the first to a distance to develop a
ture is kept at a relatively low temperature through in is hydrostatic pressure of the liquid contained in the first
direct heat exchange in the cooling device by means of a Zone of about 0.5 to 2 kg/cm. above atmospheric pres
heat-removing fluid, frequently requiring the use of a Stre.
refrigeration unit since running water, which would be 50 In accordance with our invention, we are able to take
the preferred heat-removing fluid, is not always at a suf- 3: advantage of the quickness of condensation at high tem
ficiently low temperature at all seasons of the year. In peratures and thus to effect a great part of the aldoliza
this French patent, the conversion rate is controlled as a tion in a very short time and in a very small fraction of
function of the temperature and it is required that the the travel of the reaction mixture. The operation is
higher the temperature, the smaller should be the rate of 55 thus conducted in a reduced space and the reaction is
carried out without substantial formation of the unde
conversion in order to avoid the production of high boil sired higher boiling by-products. A high conversion rate
ing products with consequent fall of yield. Working at of acetaldehyde into acetaldol is obtained and the total
a temperature of 35 C., a conversion rate of 40% is not duration
to be exceeded, according to this French patent. That required inofprior the aldolization is much shorter than that
processes. Thus, the total duration can
part of the system where the acetaldol is principally 60
formed is operated according to the French patent at a be and preferably is less than six minutes.
preferred temperature of 27 C.-30°C. and the mixture The temperature range of the reaction in the first stage
is thereafter cooled by water in the subsequent stage at in accordance with our process is preferably from 40° C.
15° C.-30° C. A considerable drawback in the practice to 50° C. and in the second stage from 20° C. to 35° C.
of processes such as described in this French patent is 65 Accordingly, there is no difficulty in using running water
that in order to obtain conversion to acetaldol without without refrigeration even under summertime conditions,
producing large quantities of undesired by-products, the i; in accordance with our invention.
acetaldehyde must remain from 20 minutes to two hours In operating the process continuously, the heat evolved
in the apparatus. Furthermore, the apparatus is bulky in the first zone must be removed quickly. For this pur
and the fact that the temperatures must be kept low 70 pose, the mixture is preferably passed through this first
means that a refrigerating unit must be included in the Zone so that it offers as large a heat exchange surface as
possible with respect to its volume and the heat-remoy
 2,718,598 4
3 area. A pressure of inert gas, such as nitrogen, may be
ing fluid employed for the heat exchange is renewed as established in vessel 7 when it is desired to establish the
quickly as possible. required pressure on the mixture in the first stage other
In the preferred embodiment of our invention as shown wise than hydrostatically or to increase the hydrostatic
in the drawing discussed below, the body of acetaldehyde pressure
acetaldol-catalyst mixture is circulated rapidly through Pipe 1 on said mixture.
is covered with a cooling jacket 11 Supplied by
a system having substantially constant cross section. piping 12 connected at the upper extremity of the U and
Thus the System may be and preferably is as shown in pipe 13 connected at the lower extremity of the U, each
the drawings, a narrow piping having a substantially uni of these pipes being connected to a pump 14 for circulat
form cross section. The circulating mixture is contin O ing the water or other cooling fluid through the jacket 11.
uously fed with acetaldehyde and aldolization catalyst The pipe 15 is connected near the pump to line 13 for
while a withdrawal of a quantity of mixture correspo ind introducing fresh cold water and pipe 16 is connected
ing to the feed is effected. An indirect heat exchange is to line 13 at a point more remote from the pump for
established between the mixture that circulates through removing warm water from the circulating System. Cir
the system and the heat-removing fluid which is preferably culation is counterclockwise through the pipe 12, jacket
water. The speed of circulation of the mixture and the 1, and return pipe 13 to the pump 14.
speed of passage of the fluid are regulated with respect Piping 6 is also almost completely covered with cool
to each other and with respect to the rate of feed so that ing jackets. As shown in the drawing, this piping 6 has
the temperature of the circulating mixture of acetalde zigzag form and the cooling jacket comprises a number
hyde, acetaldol and catalyst remains substantially con 20 of sections 17, one for each branch of the zigzag piping
stant at the level in the range at least 40° C. to about 6. These sections are interconnected in series by joints
50° C. (first zone) or about 20° C. to 35° C. (second 18 and the cooling jacket system is connected to pipe 19
Zone). The circulation is further regulated so that the through which water or other cooling fluid flows to the
time necessary for the mixture to travel through the first pump 20 and pipe 2i. The pipe 21 joins the last of the
Zone does not exceed one minute. The provision of 25 series of cooling jackets 17 at the top of the ZigZag Se
aldolization chambers of Substantially uniform cross sec ries. The pipe 19 joins the first or bottom of the jackets
tion insures substantially constant high linear speeds of 17 at the bottom of the series. The circulation as shown
the circulating mixture throughout the two zones, which through the water jackets and pump is counterclockwise
has not been the case in prior systems. The heat-remov in this system also. Pipe 22 supplies cold water to this
ing fluid such as water is circulated through the system 30 system and pipe 23 withdraws warm water from the Sys
which is fed continuously with the cold fluid while a cor tem, both being connected to the pipe 19 as shown.
responding amount of warm fluid is withdrawn. Thermometer 24 is located at the outlet of the lower leg
For establishing the required pressure of about 0.5 of U-tube 1. Thermometer 25 is located in pipe 6 as it
kg./cm. to 2 kg./cm., any suitable means known in the passes into the first of the jackets 17. Thermometer 26
art may be used such as a pressure of inert gas established 35 is located in the pipe 6 just beyond the exit of this pipe
on the liquid in the system. However, in accordance with from the uppermost jacket 17. Thermometers 27 and 28
our invention, it is especially advantageous to establish are provided, respectively, in the cooling systems of the
this pressure at least in part as a hydrostatic pressure. first and second zones and thermometers 29 and 30 are
For this purpose, as pointed out above, the mixture in located respectively in the cold water entrance pipes of the
the Second Zone of aldolization which is at a lower ten 40 first and second Zone cooling Systems.
perature is caused to travel upwards. On account of the Alterations may be made in the above apparatus with
fact that the time for which the mixture must be main out departing from the invention; for instance, instead
tained at this temperature is relatively long and that the of having single pipes 1 and 6, such pipcs may be replaced
specific weight of the mixture increases as the adoliza by a bundle of pipes in each instance.
tion progresses, so that the specific weight of the mixture 45 The following are examples of the process as it may
travelling upwardly in the second zone is higher at the be carried out in connection with the apparatus as de
top of this zone and lower at the bottom thereof, the scribed. It is to be understood that the examples are
length of the piping constituting the second zone may be illustrative and the invention is not to be considered as
considerably greater than would be necessary for estab restricted thereto except as indicated in the appended
lishing the required hydrostatic pressure, and it may be 50 claims.
advantageous, to avoid too high hydrostatic pressure, to Example I
give the piping constituting the second zone a sinuous
form. The first aldolization zone consisting of the interior
An apparatus which may be employed in carrying out of piping 1, 2 and pump 3 has a volume of 9 liters. The
the above-described process is shown in the accompany reaction mixture of acetaldehyde, acetaldol and aldoliza
ing drawing, wherein the figure shows diagrammatically tion catalyst is circulated through this Zone, by pump 3,
the apparatus employed. at the rate of about 25 cubic meters per hour. Cooling
Referring now to this apparatus, a system having a water is circulated by pump 14 through the cooling system
Small vertical height is shown at the bottom of the draw including water-jacket 11, pipe 13, pump 14 and pipe 12
ing. It has a preferably U-shaped portion designated as 60 at the rate of 30 cubic meters per hour. Acetaldehyde
1. The ends of this U-shaped portion are connected by is fed through pipe 4 into pipe 2 at the rate of 800 liters
piping 2 leading to a pump 3 for circulating the acetalde per hour, i. e., 625 kilograms per hour, and an aqueous
hyde-acetaldol-catalyst mixture through 1. Pipe 4 sup solution of sodium hydroxide is fed through pipe 5 into
plies acetaldehyde to pipe 2 and pipe 5 supplies sodium pipe 2 at the rate of 200 liters per hour. This aqueous
hydroxide solution. The piping i, 2 and pump 3 con sodium hydroxide solution contains 1300 grams of sodium
stitute the first aldolization zone which includes the afore hydroxide and is in the form of a 0.65% solution in water.
mentioned elongated path of restricted cross-sectional There is thus fed 2.1 grams of sodium hydroxide per kilo
area. Leading from pipe 2 situated as here shown be gram of acetaldehyde.
tween the lower leg of the U and the pump is a pipe 6 The temperature as shown on thermometer 24 of the
leading upwards through a series of water-jackets to 70 reaction mixture circulating through the first Zone is
approximately the center of an acidification vessel 7. maintained at about 45° C. The temperature as shown
Acid is added to this vessel through a pipe 8. The vessel on thermometer 29 of the water introduced into the cool
is fitted with a vent 9 and from the bottom thereof raw ing system is 20° C. The temperature as shown on ther
aldol is withdrawn through a pipe 10. Pipe 6 constitutes mometer 27 of the water at the exit from pipe 13 is 38
the Second aldolization zone which includes the afore C. The heat evolved by the reaction is absorbed by the
mentioned elongated path of restricted cross-sectional
 5 2,718,598
circulating water, cooling water being introduced through 6
pipe 15 into the
moved by pipe 16.system. The excess of warm water is re sponds to a conversion rate of 40%. The pressure is
maintained at about 1.6 kg/cm. above atmospheric pres
The specific weight of the liquid in the first Zone is ture. The time of contact between acetaldehyde and
950 at 45° C. and its content in aldol is 22%, which catalyst in the first zone is 25 seconds.
corresponds to a conversion rate of 29%. The pressure Cooling water for the second aldolization Zone is cir
is at about 1 kg./cm. above atmospheric pressure to pre culated by pump 20 at the rate of 30 cubic meters per
vent the reaction mixture from boiling. The time of con hour. The temperature as shown on thermometer 25 is
tact between acetaldehyde and catalyst in this first Zone is about 50° C. The temperature as shown on thermom
37 seconds.
eter 26 is 20° C. The temperature as shown on ther
The second reaction zone consisting of the interior of on mometer 30 is about 15° C. The temperature as shown
the thermometer 28 is 20° C.
pipe 6 has a volume of 65 liters. The reaction mixture
of acetaldehyde, acetaldol and aldolization catalyst issuing The specific weight of the liquid at the exit from the
from the first zone travels ascendantly through the sec second reaction zone is 1.036 at 20° C. and its content
ond zone from pipe 2 to vessel 7. Cooling water is cir in aldol is 41%, which corresponds to a conversion rate
culated by pump 20 through the cooling system including 5 of 55%. The time of contact in the second zone is about
water-jackets 17, pipe 19, pump 20 and pipe 21 at the 3 minutes and 10 seconds.
rate of 30 cubic meters per hour. The aldolization reaction is stopped as in Example 1.
The temperature as shown on thermometer 25 of the The raw aldol was analyzed by crotonization. One
reaction mixture at the entrance thereof into the jacketed kilogram of raw aldol containing unconverted acetalde
part of pipe 6 is 45.5° C. The temperature as shown on 20 hyde, neutralized catalyst, water, etc. resulting from the
thermometer 26 of the reaction mixture at the exit from under use of 756 grams of acetaldehyde, gave after crotonization
the jacketed part of pipe 6 is 35 C. The temperature analysis: pressure in the presence of acid, the following
as shown on thermometer 30 of the water introduced into
the cooling system is 20° C., and the temperature as Unconverted acetaldehyde ---- 340 grams
shown
pipe 19 on thermometer
is 29° C. 28 of the water at the exit from Pure crotonaldehyde --------- 320 grams (correspond
The specific weight of the liquid at the exit from the sec ing to 402 grams of
ond reaction zone, that is liquid emerging at the upper acetaldehyde)
end of pipe 6 is 1.015 at 35 C. and its content in aldol 96.75%. Thus, the conversion rate is 55% and the yield is
is 38%, which corresponds to a conversion rate of 50%. 30
Theseconds.
40 time of contact in the second zone is 4 minutes and Example 3
At the outlet of this second zone, acid is added by pipe in The process is carried out in the same apparatus and
the the
samefollowing:
manner as in Example 1, the numerical data
8 in the acidification vessel 7 to stop the condensation 35 being
reaction by reducing the pH of the mixture to 7-7.5 pH. The reaction mixture of acetaldehyde, acetaldol and
The raw aldol is drawn off through pipe 10. aldolization catalyst is circulated through the first aldoli
The raw aldol was analyzed by crotonization. One zation
kilogram of raw aldol containing unconverted acetalde Coolingzone at the rate of 25 cubic meters per hour.
hyde, neutralized catalyst, water, etc. resulting from the 40 by pump 14 atforthetherate
water first aldolization zone is circulated
use of 756 grams of acetaldehyde, gave after crotoniza Acetaldehyde is fed at theofrate 30 cubic meters per hour.
of 600 liters per hour,
tion under
analysis: pressure in the presence of acid, the following i. e., about 469 kilograms per hour. The aqueous solu
tion of sodium hydroxide is fed at the rate of 200 liters
Unconverted acetaldehyde. 378 grams per hour, containing 1200 grams of sodium hydroxide,
Pure crotonaldehyde-------, 295 grams (corresponding 45 this solution being thus in the form of a 0.6% solution in
water. There
to 370 grams of acetalde hydroxide is thus fed
per kilogram about 2.5 grams of sodium
of acetaldehyde.
hyde)
Thus, the conversion rate is about 50% and the yield is The temperature as shown on thermometer 24 is main
98%. Small amounts of by-products not exceeding 2% 50 tained mometer
at 42 C. The temperature as shown on ther
29 is about 25 C. The temperature as shown
of the aldehyde converted were formed in the reaction. on thermometer 27 is 37° C.
The unconverted aldehyde may be recovered from the The specific weight of the liquid in the first Zone is
raw aldol by
circulation well-known
through pipe 4. methods and returned for re corresponds
951 at 42 C. and its content in aldol is 17.5%, which
to a conversion rate of 25%. The pressure
Example 2 55 is maintained at about 0.8 kg/cm. above atmospheric
The process is carried out in the same apparatus and catalyst pressure. The time of contact between acetaldehyde and
in the first zone is 45 seconds.
in thethe
being same manner as in Example 1, the numerical data
following: Cooling water for the second aldolization Zone is cir
The reaction mixture of acetaldehyde, acetaldol and al hour. culated by pump 20 at the rate of 30 cubic meters per
dolization catalyst is circulated through the first aldoliza 60 42.5 The temperature as shown on thermometer 25 is
tion Zone, by pump 3, at the rate of about 35 cubic meters C. The temperature as shown on thermometer 26
per hour. Cooling water for the first aldolization zone is 30° C. The temperature as shown on thermometer 30
is circulated by pump 14 at the rate of about 25 cubic is 25
is C.
26 C. The temperature as shown on thermometer 28
meters per hour. Acetaldehyde is fed at the rate of 1200 65 The specific weight of the liquid at the exit from the
liters per hour, i. e., about 938 kilograms per hour. The second reaction zone is 1.024 at 30° C. and its content
aqueous solution of sodium hydroxide is fed at the rate of
300 liters per hour, containing 1950 grams of sodium of aldol
hydroxide.
in is 36.5%, which corresponds to a conversion rate
52%. The time of contact in the second Zone is about
5 minutes and 50 seconds.
The temperature as shown on thermometer 24 is main The aldolization reaction is stopped as in Example 1.
tained at about 50° C. The temperature as shown on 70 The
thermometer 29 is about 15° C. The temperature as kilogramrawof aldol
shown on thermometer 27 is 35 C.
was analyzed by crotonization. One
raw aldol containing unconverted acetalde
hyde, neutralized catalyst, water, etc. resulting from the
The specific weight of the liquid in the first zone is .955 use of 700 grams of acetaldehyde, gave after crotoniza
at 50 C, and its content in aldol is 30%, which corre 75 analysis:
tion under pressure in the presence of acid, the following
 2,718,598 8
7 ond zone directly connected with said first Zone, said sec
Unconverted acetaldehyde ---- 336 grams ond zone including an elongated path of restricted cross
Pure crotonaldehyde --------- 285inggrams (correspond
to 357 grams of sectional area, at a temperature materially below 40 C.
acetaldehyde) in the range of about 20° C. to about 35° C. for a period
such that the total residence time in said Zones does not
The conversion rate is 52% and the yield is 98%. exceed
5. Aabout 6 minutes
continuous 35 seconds.
process for producing acetaldol which
What we claim is:
1. A continuous process for producing acetaldol which comprises, continuously circulating a liquid mixture of
comprises continuously flowing a liquid mixture of acetal acetaldehyde, acetaldol and aldolization catalyst at high
dehyde, acetaldol and aldolization catalyst through a first speed through a circuit, including an elongated path of
zone, including an elongated path of restricted cross-Sec restricted, substantially constant cross-sectional area, at a
tional area, at a temperature between 40 C. and about temperature somewhat above 40 C., and in the range up
45° C. at a pressure to prevent boiling for a period of not to about 45° C., at a pressure of about 0.5 to 2 kg/cm.
over one minute to cause aldolization to begin and con above atmospheric pressure, continuously feeding the cir
tinuously passing the so-treated liquid through a Second culated mixture with acetaldehyde and aldolization cata
zone, including an elongated path of restricted cross-sec lyst, continuously passing a quantity of mixture corre
tional area, at a temperature materially below 40 C. in sponding to the feed upwardly through a Zone including an
the range of about 20° C. to about 35° C. for a period elongated path of substantially the same constant cross
such that the total residence time in said Zones does not section as the circuit and directly connected with said cir
cuit, at a temperature materially below 40° C., in the
exceed about 6 minutes 35 seconds. range of about 20 C. to about 35° C., to a height to
2. A process in accordance with claim 1 in which sub develop said pressure as hydrostatic pressure, and regu
stantially a constant volume of liquid is passed through the lating the speed of circulation of the liquid mixture in the
first zone and is cooled by a heat-removing fluid traveling circuit and the rate of feed of acetaldehyde and aldoliza
at a sufficient rate to maintain a substantially constant tion catalyst so that the time of residence of each part of
temperature in the first Zone. the liquid mixture does not exceed one minute in said cir
3. A continuous process for producing acetaldol which cuit and that the total residence time in said circuit and
comprises, continuously flowing a liquid mixture of acet said zone does not exceed about 6 minutes 35 seconds.
aldehyde, acetaldol and aldolization catalyst through a 6. The process of claim 5, the temperature in the cycle
first zone, including an elongated path of restricted cross being controlled by establishing an indirect heat exchange
sectional area, at a temperature somewhat above 40 C. between 30
the circulated mixture and a heat-removing fluid,
and in the range up to about 45° C., at a pressure to pre
vent boiling at such temperature for a period of not over preferably water. of claim 6, said heat-removing fluid
7. The process
one minute, and passing the so-treated liquid continuously being continuously circulated through a heat-removing
into a second zone, including an elongated path of re 5 fluid cycle which is put in indirect heat exchange relation
stricted cross-sectional area, connected directly with the
first zone at a temperature materially below 40 C., in the ship with the circulated liquid mixture of acetaldehyde,
acetaldol and aldolization catalyst, said heat-removing
range of about 20° C. to about 35° C. for a period such fluid cycle being fed continuously with cold fluid while a
that the total residence time in said Zones does not exceed
about 6 minutes 35 seconds, and causing it to flow up corresponding withdrawal of warm fluid is made.
wardly above the first zone to a height sufficient to develop 40 References Cited in the file of this patent
the said pressure as hydrostatic pressure in said first Zone. UNITED STATES PATENTS
4. A continuous process for producing acetaldol which
comprises, continuously flowing a liquid mixture of acet 1,075,284 Crockett ----------------- Oct. 7, 1913
aldehyde, acetaldol and aldolization catalyst through a 45 2,375,730 Caldwell et al. ------------ May 8, 1945
first zone, including an elongated path of restricted cross 2,428,846 Hull ------------------- Oct. 14, 1947
sectional area, at a temperature somewhat above 40 C. 2,468,710 Hull ------------------- Apr. 26, 1949
and in the range up to about 45 C., at a pressure of about 2,489,608 Alheritiere ------------- Nov. 29, 1949
0.5 to 2 kg./cm.2 above atmospheric pressure for a period 2,517,013 Miller et al. -------------- Aug. 1, 1950
of not over one minute to cause aldolization to begin, and
passing the so-treated liquid continuously through a sec