June 27, 1933. P. J.

CARLISLE 1,915,354
MANUFACTURE OF CHLOROFORM
Filed Oct, 8, 1930.

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 Patented June 27, 1933 1,915,354

UNITED STATES PATENT OFFICE

W PAUL JOHNSON CARLISLE, OF NIAGARA FALLS, NEW YORK, ASSIGNOR, BY MESNE AS
SIGNMENTs, To E. I. DU PONT DE NEMOURS AND COMPANY, A CORPORATION OF
DELAWARE
MANUFACTURE OF CHLOROFORM
Application filed October 8, 1930. Serial No. 487,152.
This invention relates to the manufacture hyde with a hypochlorite by keeping both
of chloroform by the treatment of organic the concentration of hypochlorite and the
carbonyl compounds with aqueous. Solutions relative proportions of the reactants fairly
containing active chlorine. More particu constant during the reaction; by avoiding a
5 larly, it relates to the production of chloro large excess of either reactant; by mixing the 55
form by the reaction of hypochlorite with reactants quickly and thoroughly at a tem
ketones or aldehydes. - perature above 60° C., and by removing the
Various processes for the chlorination of chloroform from the reaction mixture prac
ii) aldehydes or ketones by means of hypochlo
rite solutions have been proposed, which give
tically as fast as it is formed. Such condi
tions exist when the reactants are continu 60
low yields of chloroform. ously and simultaneously added to a mixing
My experimental work has led me to believe vessel and the chloroform is continuously
that there are several possible explanations removed from the reaction mixture.
of the low yields obtained in these prior batch The figure in the attached drawing shows
processes. In the first place, when one diagrammatically an apparatus suitable for 65
reactant is passed into a large body of the carrying out the invention. 1 is a reservoir
other, there is at first an excess of one reac equipped with an air inlet 2 and liquid outlet
tant which is too large for the best results. 3. 4 is an auxiliary reservoir connected to 3,
1:30 Another possible cause of low yield is the provided with stopcock 5, and joining flow
' decrease of hypochlorite ion concentration meter 6. Tubes 7 and 12 connect flowmeter 6 0
and the corresponding increase in the hydrox with the lower portion of the reaction vessel
ide concentration as the reaction proceeds. 16. 8, 9, 10, and 11 form a similar parallel
The hydroxide may cause condensation or System comprising an auxiliary reservoir,
23
polymerization of the unreacted carbonyl stopcock, flowmeter and tube also connected to
compound or, hydrolysis of the chloroform. the lower portion of vessel 16. Reaction ves 5
The lowered concentration of hypochlorite Sel 16 is provided with agitator 14 driven by
ions also probably decreases the speed of the motor 15. Wessel 16 is also provided with
main reaction and thus favors undesirable steam inlet 13 and thermometer 17. Tube 18
side reactions. - joins the upper portion of reactor 16 to still
One object of this invention is to provide a 19. Tube 2 leads within the still and there 80
continuous and efficient process for the manu ends in perforated tube 22; a thermometer 20
facture of chloroform from organic carbonyl is also inserted in still 19. The exit of still 19
compounds such as an aldehyde or a ketone. connects with a trap or separator 24 having
A further object is to provide a method of a vapor outlet 25 and liquid outlet 23.
85 utilizing “liquid bleach' and “liquid bleach One way of carrying out this invention will 85
sludge', a by-product occurring in the manu now be described by reference to the drawing.
facture of “liquid bleach', as sources of hypo The hypochlorite reservoir 1 is charged with
chlorite for the manufacture of chloroform. a hypochlorite solution. If liquid bleach
“Liquid bleach', designates the calcium
40 hypochlorite solution obtained by treating sludge is used, air is forced in through tube 90
milk of lime with chlorine and subsequently 2 to maintain the solids in suspension or me.
separating solids. "Liquid bleach sludge’ chanical agitator may be used. The liquid
passes through the tube 3 into the auxiliary
consists of “liquid bleach” mixed with solids, reservoir 4, and thence through the flow meter
25 such as calcium carbonate and undissolved 6 and tubes 7 and 12 into the reaction cham
calcium hydroxide. These solids appear to ber 16. The rate of flow is controlled by 95
behave as inert material in my herein de stopcock 5. -
scribed process. Either acetone or acetaldehyde, preferably
I have now found that chloroform may be in aqueous solution, is charged into reser
obtained in good yield by the reaction of a
50 carbonyl compound, voir 8, from whence it passes through the
such as a ketone or alde flow meter 10, and tube 11 to the reaction 100
 2 1,915,354
the steaming device must of course be main
chamber 16. Its rate of flow is controlled by tained
stopcock 9. - above the boiling point of chloro
The two liquids enter the reaction chamber form, and preferably at 80-100° C. Means
16 by way of the concentrically arranged of heating and agitating other than the de
tubes 11 and 12 and are thoroughly mixed by scribed introduction of steam may be em 70
the agitator 4. Stean is introduced through. ployed to remove chloroform from the reac
the tule 13 at such a rate as to maintain the tion residues. In place of the horizontal
teimperature of the reaction mixture, indicat steamer. 19, a vertical, packed or baffled tower
ed by the thermometer 17, at about 70° to in which the reaction residue, introduced at 75
10 SOo C. .. . - - . .- - the top, flows counter current to steam intro
The reaction residue, which is a sludge duced at the bottom, and chloroform and wa
or slurry if bleach sludge is used, overflows ter vapor are led off through a connection at
through tube 18, accompanied by chloroform the top, may be used, but if the process is car
and water vapors, into the steamer 19, Steam, ried out with liquid bleach sludge, the pack 80
5 flowing through tube 21, is forced through ing or baffles must be such as will not cause
the perforated tube 22 covered by the residue. clogging. .... . . . .
The steam keeps, the residue thoroughly agi As raw materials any aldehyde, ketone or
tated and distills off the last traces of chloro other: organic carbonyl compound which is
form. The mixed chloroform and water va capable of reacting with a hypochlorite to 85
20 pol's and the spent residue pass into the trap produce chloroform may be employed. This
24, where they are separated, the residue pass invention is likewise not limited to the use of
ing out through tube 23 and the chloroform any solution orbutsludge
liquid bleach, may be practiced by using
containing a reactive
and water vapor's passing through tube 25 to hypochlorite, for instance sodium hypochlo
a suitable condenser. The condensate forms 90
two layer's on standing, and the chloroforn rite. ,
Apparatus for carrying out my invention
is drawn off.
The relative rates of flow of carbonyl com may be constructed of glass, iron, steel or
pound and bleach are preferably adjusted other material commonly used in chemical
so that the amount of available chlorine in manufacture and which are not injured by 95
the bleach is in about 10–25% excess over that the reactants in any suitable arrangement.
required to react with the carbonyl compound - Eacample I
and so that about 2.5 to 12.5 minutes are re A 46% aqueous solution of acetaldehyde
(Hired for the reactants to flow from the inlet was reacted with liquid bleach sludge by
to the outlet of the reaction chamber. How
35 ever, this invention is not limited to these means of the apparatus and procedure de 00

specific rates of flow of reactants since these
may be considerably varied dependent on
stirring and type of apparatus. The hypo
chlorite concentration of the bleach may also
40 Vary considerably; but I prefer to use bleach
containing hypochlorite in amounts equiva
lent to more than 40 grams per liter of avail
the chlorine. . - ". .
The temperature of the reacting materials
is preferably maintained at 70-80° C. Other
temperatures may be used, but somewhat
smaller yields are obtained if temperatures retical yield, was obtained by condensing the
below 70° C. are used. It is desirable to
maintain the reaction mixture at a tempera issuing vapors and separating chloroform 1.5
ture above the boiling point of chloroform, in
from the condensate. . . .
order to remove the product continually as
chloroform vapor. There is no apparent
advantage in using temperatures above 80°
C. The vapors may be removed from the
- 55 reaction chamber directly to a condenser,
they may be allowed to pass through the
steamer before condensation, or they may
be removed separately, from both the reaction
chamber and steamer, and condensed. . . . .
60 The process may be operated without the
steamer 19, or its equivalent; but if this is
done, a considerable amount of chloroform is
carried out with the reaction residue. This
is especially true when bleach sludge is used.
For effective operation, the temperature in
'. 65
scribed above. During a period of 50 min
utes, 197 grams of the aldehyde solution and
9,130 grams of the sludge were passed
through the reaction chamber. The avail 105
able chlorine in the sludge was 81.7 grams
per liter, which is equivalent to about 25%
excess over that theoretically required to re
act with the aldehyde. The temperature of
the reaction mixture was maintained at ll.0
about 76° C. and the temperature of the va
pors in the steamer at about 95°C. 206 grams
of chloroform, equivalent to 84% of the theo
. . ... .
- Enample II -. . . ..
The process was carried out as in Example
I, using a 45.6% acetaldehyde solution and a 20
clear calcium hypochlorite solution instead
of liquid bleach sludge. During a period of
70 minutes, 290 grains of the acetaldehyde
solution and 18,950 grams of calcium hypo
chlorite solution containing 80 grams of 125
available chlorine per liter were passed
through the reaction chamber. The reac
tion temperature was maintained at about
79° C. and the steamer temperature at about
90° C. 314 grams of chloroform, equivalent
to 88% of the theoretical yield, were obtained.
 1,915,354 3
Eacample III hypochlorite, said excess being equivalent to
A 60% aqueous solution of acetone was not more than about 25% excess of available
chlorine, thoroughly and substantially in
reacted with clear liquid bleach by means of
the apparatus and procedure described stantaneously mixing them, heating the mix
ture to a temperature of 70-80° C. while con
above. During a period of 60 minutes, 365.9 tinuously
grams of the acetone solution and 13,164. form therefrom, removing vapor containing chloro
grams of the bleach were passed through the agitating the residue additionally heating and
to separate further
reaction chamber. The available chlorine in chloroform as vapor, condensing
O the bleach was 79.7 grams per liter, which said vapor's
is equivalent to about 15% excess over that and mechanically separating liquid chloro 5

theoretically required to react with the ace form5.

from the condensate.
Process for manufacture of chloroform
tone. The temperature of the reaction mix comprising continuously flowing together as
ture was maintained at about 1° C. and the
5 temperature of the vapor's in the steamer a liquids acetaldehyde and a hypochlorite solu 80
tion, the relative proportions of said hypo
about 95° C. 404 grams of crude chloro chlorite
form were obtained by condensing the issuing and acetaldehyde being maintained
Vapoi's and separating the chloroform from substantially
of either
constant without a large excess
reactant, thoroughly mixing them,
the condensate. The crude chloroform was
20 distilled and 393.8 grains of chioroform were heating the mixture, continuously removing 85
obtained, equivalent to about 87% of the the vapor containing chloroform therefrom, con
oretical yield, calculated from the amount of densing said vapor and mechanically sepa
rating liquid chloroform from the conden
acetone used.
In the claims, “calcium hypochlorite solu sate. 6. Process for manufacture of chloroform
25 tion” is intended to include any solution, such 90
comprising continuously flowing together as
as liquid bleach, which contains calcium hy liquids acetaldehyde and a calcium hypochlo
pochlorite. Similarly, “hy Eochlorite solu rite solution, said hypochlorite
tion’ includes any solution containing hypo tained being main
chlorite whether pure or not. in a constant excess of not more than
- about 25%,
30 claim : thoroughly and substantially in
1. Process for manufacture of chloroform stantaneously mixing them, heating the mix
ture to a temperature of 70-80° C., continu
comprising continuously flowing together as ously
liquids a hypochiorite solution and an or removing vapor containing chloroform
ganic carbonyl compound capable of react from the mixture, condensing said vapor and
35 ing with hypochlorite to produce chloroforn mechanically separating liquid chloroform 00
while maintaining the relative proportions from the condensate.
of hypochlorite and carbonyl compound form 7. Process for continuously
the manufacture of chioro
substantially constant and avoiding a large er as comprising flowing togeth
liquids acetaldehyde and a calcium hy
excess of either reactant. pochlorite solution at such relative rates that
, 40 2. Process for the manufacture of chloro 05
form comprising continuously flowing to there is an excess of available chiorine, said
gether as liquids a hypochlorite solution and excess being from 10–25%, thoroughly and
an organic carbonyl compound capable of re substantially instantaneously mixing them,
acting with hypochlorite to produce chloro heating the mixture and continuously remov
45 form, at such relative rates that there is an ing vapor containing chloroform therefrom. O
excess of available chlorine, said excess being 8. Process for manufacture of chloroform,
comprising continuously flowing together as
from 10 to 25%. .
3. Process for the manufacture of chloro liquids acetaldehyde and a calcium hypochlo
form comprising continuously flowing to rite solution at such relative rates that there
50 gether as liquids a calcium hypochlorite so is an excess of available chlorine, said excess
lution and an organic carbonyl compound being from 10 to 25%, thoroughly and sub
capable of reacting with hypochlorite to stantially instantaneously mixing them, heat
produce chloroform at such relative rates ing the mixture to a temperature of 70-80°
that there is an excess of available chlorine, C. and continuously removing vapor con
55 said excess being 10–25%, thoroughly and taining chloroform from the mixture. 20
substantially instantaneously, mixing them, 9. Process for manufacture of chloroform
heating the mixture and continuously remov comprising continuously flowing together as
ing vapor containing chloroform from said liquids acetaldehyde and a calcium hypochlo
mixture. rite solution, said hypochlorite being main
60 4. Process for manufacture of chloroform tained in a constant excess of not more than 25
comprising continuously flowing together as about 25%, thoroughly and substantially in :
liquids a calcium hypochlorite solution and stantaneously mixing them, heating the mix
an organic carbonyl compound capable of ture to a temperature of 70-80° C., maintain
reacting with hypochlorite to produce chloro ing the mixture at said temperature for 2.5- 30
form while maintaining a constant excess of 12.5 minutes while continuously removing
 4. ... 1,915,354

vapor containing chloroform from the mix renoving vapor containing chloroform from
ture, additionally heating and agitating the the mixture, condensing said vapor and me
residue to remove further chloroform as va chanically separating liquid chloroform from
por, condensing said vapors and mechanical the15.condensate.
Process for manufacture of chloroform 70
ly separating liquid chloroform from the comprising continuously flowing together as
condensate. -
10. Process for manufacture of chloroform liquids acetone and a calcium hypochlorite so
comprising continuously flowing together as lution at such relative rates that there is an
liquids acetaldehyde and a calcium hypochlo excess of available chlorine, said excess being
0 rite solution containing suspended solids, said from 10 to 25%, thoroughly and substantially 75
hypochlorite being maintained in a constant instantaneously mixing them, heating the
mixture to a temperature of 70°-80° C., and
excess of not more than about 25%, thorough continuously
ly and substantially instantaneously mixing chloroform from removing vapor containing
them, heating the mixture to a temperature 16. Process for the mixture.
manufacture of chloroform
of 70-80° C., continuously removing vapor comprising continuously flowing together as
containing chloroform from the mixture, con liquids acetone and a calcium hypochlorite
densing said vapor and mechanically sepa
rating liquid chloroform from the conden in a constant excess of not more maintained
Solution, said hypochlorite being
than about
Sate.
11. Process for manufacture of chloroform 25%, thoroughly and substantially instan 85
comprising continuously flowing together as taneously mixing then, heating the mixture
liquids acetaldehyde and a calcium hypochlo to a temperature of 70°-80° C., maintaining
rite solution containing suspended solids at the mixture at said temperature for 2.5-12.5
minutes while continuously removing vapor
such relative rates that there is an excess of 90
containing chloroform from the mixture,
available chlorine, said excess being from 10 additionally
to 25%, thoroughly and substantially instan heating and agitating the resi
due to remove further chloroform as vapor,
taneously mixing them, heating the mixture contensing
to a temperature of 70–80° C., and continu separating liquid said vapors and mechanically
ously removing vapor containing chloroform densate. chloroform from the con 95
from the mixture. .
17. Process for manufacture of chloroform
comprising continuously flowing chloroform
12. Process for manufacture of together as colmprising continuously flowing together as
liquids acetaldehyde and a calcium hypochlo liquids acetone and a calcium hypochlorite
- Y-
rite solution containing suspended solids, said solution containing suspended solids, said hy
pochlorite being maintained in a constant 100
hypochlorite being maintained in a constant excess
excess of not more than about 25%, thorough ly andofsubstantially
not more than about 25%, thorough
instantaneously mixing
ly and substantially instantaneously mixing
them, heating the mixture to a temperature them, heating continuously
the mixture to a temperature
removing vapor
of 70-80° C., maintaining the mixture at said of 70-80° C.,
20 temperature for 2.5-12.5 minutes, continu containing chloroform from the mixture, con 105
ously removing vapor containing chloroform densing said vapor and mechanically separat
from the mixture, additionally heating and ing18.liquid chloroform from the condensate.
Process for manufacture of chloroform
agitating the residue to remove further chlo comprising continuously flowing together as
roform, condensing said vapors and mechani liquids acetone and a calcium hypochlorite O
cally separating liquid chloroform from the solution containing suspended solids at such
condensate. . relative rates that there is an excess of avail
comprising continuously flowing chloroform
13. Process for manufacture of together as able chlorine, said excess being from 10 to
liquids acetone and a hypochlorite solution, 25%, thoroughly and substantially instan
the relative proportions of said hypochlorite taneously mixing them, heating the mixture 5
and acetone being maintained substantially to a temperature of 70-80° C. continuously
constant without a large excess of either re removing vapor containing chloroform from
actant, thoroughly mixing them, heating the the mixture, additionally heating and agitat
mixture, continuously removing vapor con ing the residue to remove further chloroform
taining chloroform therefrom, condensing as vapor, condensing said vapors and me 120
said vapor and mechanically separating lic chanically separating liquid chloroform from
uid chloroform from the condensate. the condensate. -
19. Process for manufacture of chloroform
14. Processcontinuously
comprising for manufacture of chloroform
flowing together as comprising continuously flowing together as
SO liquids acetone and a calcium hypochlorite liquids acetone and a calcium hypochlorite
solution, said hypochlorite being maintained solution containing suspended solids, said
in a constant excess of not more than about hypochlorite being maintained in a constant
25%, thoroughly and substantially instan excess of not more than about 25%, thor
taneously mixing them, heating the mixture oughly and substantially instantaneously
to a temperature of 70-80° C. continuously mixing them, heating the mixture to a tem
 1,915,354

perature of 70-80° C., maintaining the mix

ture at said temperature for 2.5-12.5 min
utes, continuously removing vapor contain
ing chloroform from the mixture, addition
ally heating and agitating the residue to re
move further chloroform as vapor, condens
ing said vapors and mechanically separat
ing liquid chloroform from the condensate.
igned at Niagara Falls, in the county of
O Niagara and State of New York this 19th
day of September A. D. 1930.
PAUL JOHNSON CARLISLE.

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