April 10, 1956

H. c. UREY

2,741,543

PROCESS FOR THE PRODUCTION OF DEUTERIUM OXIDE

Filed May 22, 1945

ENRICHD PROIDUCT
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FE D WATER

26

INVENTOR
HAROLD G. UREY
BY

AM
ATTORNEY

United States Patent G '

f.

2,741,543

C@

Patented Apr. 10, 1956

1
hydrogen sul?de.

One disadvantage that has been en

countered in the operation of dual temperature hydrogen

sul?de-water exchange systems arise out of the corro

2,741,543

sive tendency of the hydrogen sul?de. An advantage of

PROCESS FGR TEE PRODUCTIGN OF

DEUTERIUM OXIDE

using mercaptaus is that some of the mercaptans are

liquids and therefore the exchange reaction may be car

ried out in the liquid phase at atmospheric pressure. It
has been found that liquid-liquid mixtures of mercaptan

Harold C. Urey, Leonia, N. 5., assignor to the United

States of America as represented by the United States

Atomic Energy Commission

Application May 22, 1945, Serial No. 595,196

19 Claims. (Cl. 23-264)

and water have less tendency to corrode structural ma

10 terials containing iron than do mixtures of hydrogen sul

This invention relates to a deuterium concentration

process and more particularly to an improved process

?de and water. Furthermore the equipment for carrying

out the exchange reaction may be more compact where
liquid-liquid mixtures are used because the total volume
or the materials entering into the reaction is less. How
ever the exchange rate of the exchange reaction between

liquid mercaptans and liquid water is exceedingly slow;

so slow in fact as to render the process impracticable

for increasing the concentration of the deuterium-con
in the absence of a catalyst.
taining species in water by an exchange of hydrogen
It is an object or the present invention to provide an
isotopes between water and certain compounds contain
ing a hydrogen-sulfur bond.
20 improved process for increasing the concentration of the
deuterium-containing species in water.
It has been previously proposed to effect an increase
It is another object of the invention to provide an im
in the concentration of the deuterium-containing species
proved process for effecting an increase in the concen
in water by utilizing the fact that there is a preferential
tration of the deuterium-containing species in water by
equilibrium distribution of deuterium between water and
team of an exchange reaction between water and a
certain other hydrogen-containing substances and that
substance containing a hydrogen-sulfur bond.
1
this preferential distribution varies with temperature.
It is still another object of the invention to provide a
In accordance with one speci?c prior proposal the
process of Lhis character which is carried out under such
deuterium concentration in water is increased by means
conditions that the corrosive tendency of the reactants
of an exchange reaction between liquid water and hy
drogen sul?de gas in a countercurrent system compris 30 is reduced.
ing one or more pairs of stages with the two stages of

It is a still further object of the invention to provide a

each pair being maintained at different temperatures.

catalyst for increasing the exchange rate of the hydrogen

isotopes between water and a substance containing a

hydrogen-sulfur bond.
dance of deuterium may be fed into the top of an exchange
Other objects of the invention will be in part obvious
tower maintained at a relatively low temperature and 35

Thus water containing, for example, the natural abun

caused to flow down through the low temperature tower,

then into the top of a tower maintained at a relatively

higher temperature and down through the high tempera

and in part pointed out hereinafter.

The process of the present invention is based upon the
discovery that the rate of exchange of hydrogen isotopes

between water and a substance containing a hydrogen

ture tower. Hydrogen sul?de gas may be introduced at
the bottom of the high temperature tower and caused 40 sulfur bond may be substantially increased by the addi
tion of a relatively small quantity of an alkali to the
to ?ow countercurrent to the water up through the high
reactants. In one of its broader aspects the method of
temperature tower and then up through the low tempera
the invention comprises increasing the deuterium con
ture tower. Hydrogen sul?de from the top of the low
centration in water by an exchange of hydrogen isotopes
temperature tower may be returned to the bottom of the
at two di?erent temperatures between water and a sub
high temperature tower to form a closed gas cycle and
stance selected from the group consisting of mercaptans
water from the bottom of the low temperature tower is
and hydrogen sul?de. The mercaptans used preferably
rejected. The water and hydrogen sul?de are intimate
have at least three carbon atoms so that their volatility is
ly mixed in each tower to cause an exchange of hydro
gen isotopes to take place to an extent sufdcient to estab
suf?ciently low to permit liquid-liquid exchange over a
lish isotopic equilibrium between the water and hydrogen
reasonable
temperature range without the use of pres
50

sul?de.

sures higher than atmospheric pressure. This group of

In a system of this type deuterium tends to concentrate

in the water between the two temperature stages. The

mercaptans includes, for example, isopropyl mercaptan,

n-propyl mercaptan, butyl mercaptan, thiophenol and

nature of the hydrogen isotope equilibrium between the

benzyl mercaptan. The use of an alkali also increases
water and hydrogen sul?de is such that the water con
the exchange rate between Water and the normally gase
tains approximately twice as high a concentration of 55 ous mercaptans such as methyl and ethyl mercaptan as
deuterium as does the hydrogen sul?de in contact with
well as the exchange rate between hydrogen sul?de and
the water and the distribution of deuterium between the
water, but for the reasons stated above a liquid-liquid
two materials varies with temperature. The ratio of the
exchange system is preferred. The use of an alkali serves
concentration of deuterium in water to the concentration
of deuterium in hydrogen sul?de is larger at relatively 60 the dual purpose of increasing the reaction rate of the
low temperatures than it is at relatively high tempera

exchange reaction and reducing the corrosiveness of the

solution when in contact with ironcontaining structural

tures. Thus in a system of the type described the hy
materials.
drogen sul?de in the hot tower tends to strip deuterium
As conducive to a clearer understanding of the present
from the water in contact therewith and in the cold tower
the hydrogen sul?de tends to give up deuterium to the 65 invention it may be pointed out that the distribution co
water in contact therewith. The effect of these two reac

tions is to produce in the water between the two tem

perature stages a relatively high concentration of deu

terium.

It has also been proposed that an exchange reaction as 70

described be carried out using a mercaptan in place of

e?icient for the hydrogen isotope exchange reaction be

tween mercaptans and water is represented by the fol

lowing expression:
_

D/H (water)

a_D/H (mercaptan)

2,741,543
.huienaurlthe .enuutereurrentlyhewingmenweur Will

wherein:

in the tower 16 an exchange of hydrogen isotopes takes

place of such a character that deuterium is transferred
from the aqueous solution to the mercaptan. Solution de
pleted with respect to deuterium passes out of the bottom
of tower 16 through pipes-26, :flows through the heat ex

a=the distribution coef?cient.

D/H (water)r=the ratio of deuterium to the other hydro

gen isotope, sometimes called protium, in the vwater

phase.

D/H (mercaptan)=the ratio of deuterium t_o protium in

changer30 whereinit gives up some ofitssensibleheat to

the mercaptan phase. This distribution coe?icent varies

the solution flowing from tower '10 to tower '16, vand then

inversely with temperature and the measured values of

the coe?icient for isopropyl mercaptan and water at sev
eral temperatures are given in the following table.
Temp. in '0.

_a

leaves the system through pipe 34.

10

Mercaptan enriched with respect to deuterium leaves

the topof tower 16 and flows through heat exchanger38

and pipe 40 to the bottom of coidtowerl-ll). 'i-Wit-hin-the

tower 10 the mercaptan gives up deuterium to the down

wardly ?owing solution and ?ows from the top of tower
915 10 through pipe 42 to the *heat exchanger 38, thence
through pipe 24 to the bottom of tower 16. Within the
heat exchanger 38 the mercaptan from the top of the hot
tower gives up .a portion of its sensible heat to the mer

It is apparent that, assuming equilibrium distribution.

the water phase in a mixtureofwaterand mercaptan will

captan that flows from the top of the cold tower to the
20 bottom of the hot tower. Thus the upwardly ?owing-men

captan is cooled before it enters the cold tower and the

qeateinre sreaterprepertiqn eff thetetal deuterium a1 10W

temperatureethanit will art-high temperatures- Henee by

downwardly ?owing mercaptan is heated before it enters

the hot tower. The ?ow of mercaptan is such as to form

establishing a countercurrent?ow of the 'mercaptan and

a closed cycle including tower lthpipe 42, pipe 24; tower

> water-attwe .di?ereut-temperatures,atransfernf deuterium 25 1-6 and pipes 36 and 40.

from the {IHPTQZIPIHD to the water may be effected at the
2Since deuterium passes from the mercaptan to the so

lowerptemperature and ,a transfer .of deuterium ,fr-om-Ihe

lutionin tower 10 and from the solution-to the-mercaptan

water :to the mercaptan at the highertemperature with

in tower 16 the two towers operate in such manner as to

the result that-arelatively high concentration of;deuterium

produce a relatively high concentration of deuterium at

will be built :up lathe water atapoint between the tem 30 points between the two towers and therefore enriched
perature stages.
product is prcferablyrremoved at a point between the two
In.-order-.to point outmore fully the natureofthe pres
temperature stages. A portion of the solution ?owing
ent invention a preferred embodiment of the present-meth
through \pipe 28 is withdrawn through pipe 44 and ?ows
od-will-be described with reference to the accompanying
the top of cold tower '12 where it mixes with counter
drawhigwhich shows diagrammatically apparatus capable 35 to
currently ?owing mercaptan in a manner similar to the
of carrying out the method of the invention. Referring
operation of tower 10. ' From the bottom of cold tower
to the drawing, numerals 1t}, 12 and Mrdesignate exchange
12 solution flows through the heat exchanger 46 wherein
towers which operate at arelativelyilowtemperature, say
the solution is heated by steam supplied through pipe 48
25 C. and the numerals 16, 18 and 2% designate exchange
and then enters the hot tower 18 where it again enters
towers operating at a relatively higher temperature, say 40 into an exchange reaction with .cotmtercurrently ?owing
50? C. The towers 10 and 116 are interconnected in such
mercaptan. Solution from the bottom of tower :18 is re
manner'that-a countercurrent-?ow of water and a mercap
turned through pipe 50, to pipe 32 and the top of tower
tan, e. g. isopropyl mercaptan, may be established there
16.
in. The how of water and mercaptan through -the?rst two
Solution that is further enriched with respect to deuteri
45
towers :10 and 16 is, in general, as follows: Water is vin
um is withdrawn at apointbetween the towers 12 and 18
troduced into the top of the tower '16 through pipe 22 in
and supplied to the top of the cold tower 14. The opera
the-form of an aqueous solution of caustic soda containing
tiQn of towers 14 and 520 is similar to that of towers 12
about 0.1 mol per liter of caustic soda and ?ows down
and'_1'8, respectively. It is to be understood that towers
wardly through the towers 10 and '16. lsopropyl 'mercap
14 andj20 are not necessarily the last towers in the coun

tan is introduced through pipe 24 into the bottom of the

tercurrent system, but that any desired number of pairs

of hot and cold towers may be used. Deuterium-enriched
product/is withdrawn from a point between ,the last two

hot tower 16 and flows upwardly "therethrough then up

through tower 10. The caustic soda solution leaves the
bottom of tower 16 through pipe 26 and isopropyl mer
captan frornthe top of tower 10 is returned tothe bottom
of tormr 16.

temperature stages of the countercurrent system, for ex

ample, from apoint between the towers 514 and_20 through

pipe 52.
.It is to be understood that the ieregoing description

Considering the ?ow of the reacting materials in more

the tower 10 may be ,a so-called sieve-plate tower

is illustrative .only and that numerous changes may be

which, as indicated in the drawing, comprises a series of

herizantal perforated Plates provided with down pipes

frpul Que Plate to anether- Such towers are ltnewn in the
antandprovide intimate Contact between two countercur
rently-?owingliquids. In the tower 10 the upwardly ?ow

ins iseprepyl mereaptan and dewnwardly ?owing alkaline

exchange
solutionvcome
of hydrogen
into intimate
isotopes
contact
takeswith
placeone
within
another.
the tower

60

65

made in both the Process steps and the materials used.

Any Qf Various alkaliS may be used to increase the ex~
change reaction rate although caustic soda and calcium
hydroxide are usually preferred- Caleium hydroxide is
preierahlv used as a saturated solution and is somewhat
less effective than caustic soda. The preferred concen
tration of caustic soda for catalyzing the reaction usually
lies between 0:01 and 0.5 mol per liter.

10 of such a character that deuterium is transferred from

The numbers of pairs of exchange towers may be in
the mercaptan to the aqueous solution to increase the deu~
creased
to give any desired enrichment. The magnitude
terium concentration in the solution. The deuterium en
of the temperature difference between the high and low
riched solution leaves the bottom of tower 10 through pipe
28 and flows through heat exchanger 39 and pipe 32' to the 70 temperature towers is not critical and some degree of
top of hot tower 16. In the heat exchanger 30 the solu- .

enrichment may be obtained with very small temperature

tion is heated by being brought into heattransfer relation

ship with the hot solution leaving the bottom of tower 16.

di?crences. However in order to achieve a ~practicable

The tower 16 like the tower it) is provided with a series

of perforated plates to'ensure intimate contact of the so

enrichment it is desirable to maintain a relatively large

temperature difference between the towers, provided that
in cases where the exchange reaction is carried out be

2,741,543

tween two liquids the high temperature tower does not

reach a temperature which causes excessive vaporization
of the reactants.

From the above description it is apparent that the

present invention provides an e?ective method of con

centrating the deuterium-containing species in water.

6
from the group consisting of mercaptans and hydrogen
sul?de in a countercurrent system comprising a plurality.

of pairs of stages, one stage of each pair being maintained

at a relatively low temperature and the other stage of
each pair being maintained at a relatively high tempera
ture, mixing said substance and said solution intimately

in each of said stages to cause an exchange of hydrogen

The use of an alkali accelerates the hydrogen isotope
isotopes to take place between said substance and said
exchange rate between mercaptans and water to such an
solution, withdrawing solution from a point between each
extent as to permit attainment of substantial equilibrium
in a matter of seconds. It has been found for example 10 pair of temperature stages and feeding it to the low tem
perature stage of the next succeeding pair of stages, With
that a mixture of isopropyl mercaptan and a 0.1 molar
drawing solution from the high temperature stage of each
caustic soda solution attain 95% of equilibrium within
pair and re-introducing it into said system at a point
15 seconds or less. This exchange rate may be con
between the next preceding pair of temperature stages,
trasted with data reported in the literature to the eiiect
and withdrawing as product solution enriched with re
that the attainment of equilibrium between mercaptans
spect to deuterium at a point between the last pair of
and water (containing no added alkali) may require up
temperature stages of said countercurrent system.
to 10 hours.
5. The method of increasing the concentration of the
The rapid exchange rate attainable with the present
deuterium-containing species in water comprising the steps
method makes possible the use of a relatively compact
of establishing a countercurrent ?ow or" a mercaptan and
exchange system. Furthermore corrosion di?iculties are
a dilute aqueous solution of an alkali in a countercurrent
minimized by the fact that the exchange may be carried
system comprising a plurality of pairs of stages, one stage
out in the liquid phase and that the mixture is de?nitely
of each pair being maintained at a relatively low tem
alkaline. Thus the exchange towers and auxiliary equip
perature and the other stage of each pair being maintained
ment may be made of ordinary structural steel, if desired.
N) Cl at a relatively high temperature, mixing said mercaptan
I claim:
and said solution intimately in each of said stages to
1. The method of increasing the concentration of the
cause an exchange of hydrogen isotopes to take place be
deuterium-containing species in water which comprises
tween said mercaptan and said solution, withdrawing solu
establishing a countercurrent flow of a dilute aqueous
tion from a point between each pair of temperature stages
solution of an alkali and a substance selected from the
group consisting of mercaptans and hydrogen sul?de in 30 and feeding it to the low temperature stage of the next
succeeding pair of stages, withdrawing solution from the
a countercurrent system comprising at least two stages,
high temperature stage of each pair and re-introducing
mixing said substance and said solution intimately in each
it into said system at a point between the next preceding
of said two stages to cause an exchange of hydrogen
pair of temperature stages, and withdrawing as product
isotopes to take place between said substance and said
solution, maintaining said two stages at di?erent tem- H solution enriched with respect to deuterium at a point
between the last pair of temperature stages of said coun
peratures to produce different concentrations of deuterium
tercurrent system.
in said aqueous solution in said two stages to cause the
6. The method of increasing the concentration of the
concentration of deuterium in said solution to become
deuterium-containing species in water comprising the
relatively high at a point between said temperature stages,
steps of establishing a counter-current ?ow of liquid
and withdrawing at a point between said temperature
mercaptan and a dilute aqueous solution of an alkali in
stages solution that is enriched with respect to deuterium.
a countercurrent system comprising a plurality of pairs
2. The method of increasing the concentration of the
of stages, one stage of each pair being maintained at a
deuterium-containing species in water which comprises
relatively low temperature and the other stage of each
establishing a countercurrent ?ow of a mercaptan and
a dilute aqueous solution of an alkali in a countercurrent

system comprising at least two stages, mixing said mer

captan and said solution intimately in each of said two
stages to cause an exchange of hydrogen isotopes to take

pair being maintained at a relatively high temperature,

mixing said mercaptan and said solution intimately in

each of said stages to cause an exchange of hydrogen

isotopes to take place between said mercaptan and said
solution, withdrawing solution from a point between each
place between said mercaptan and said solution, main
taining said two stages at di?erent temperatures to pro 50 pair of temperature stages and feeding it to the low tem
perature stage of the next succeeding pair of stages, with
duce di?erent concentrations of deuterium in said aqueous
drawing solution from the high temperature stage of each
solution in said two stages to cause the concentration
pair and re-introducing it into said system at a point be
of deuterium in said solution to become relatively high
tween the next preceding pair of temperature stages, and
at a point between said temperature stages, and with
drawing at a point between said temperature stages solu 55 withdrawing as product solution enriched with respect to
tion that is enriched with respect to deuterium.
deuterium at a point between the last pair of temperature
3. The method of increasing the concentration of the
stages of said countercurrent system.
deuterium-containing species in water which comprises
7. The method of increasing the concentration of the
establishing a countercurrent flow of a liquid mercaptan

deuterium-containing species in water by establishing a

and a dilute aqueous solution of an alkali in a counter

countercurrent ?ow of a dilute aqueous solution of an

alkali and a substance selected from the group consisting
of mercaptans and hydrogen sul?de at two di?erent tem

current system comprising at least two stages, mixing

said mercaptan and said solution intimately in each of
said two stages to cause an exchange of hydrogen isotopes
to take place between said mercaptan and said solution,
maintaining said two stages at diiferent temperatures to 65

produce di?erent concentrations of deuterium in said

perature stages which comprises causing said solution

to flow ?rst through the low temperature stage and then

through the high temperature stage, causing said sub

stance to ?ow ?rst through the high temperature stage

aqueous solution in said two stages to cause the concen
and then through the low temperature stage, mixing said
tration of deuterium in said solution to become relatively
substance with said solution intimately in each of said
high at a point between said temperature stages, and
withdrawing at a point between said temperature stages 70 two stages to cause an exchange of hydrogen isotopes to
take place between said substance and said solution, con
solution that is enriched with respect to deuterium.
tinuously re-circulating said substance from said low tem
4. The method of'increasing the concentration of the
perature stage to said high tem erature stage, withdrawing
deuterium-containing species in Water comprising the
from said high temperature stage solution that is depleted
steps of establishing a countercurrent ?ow of a dilute
aqueous solution of an alkali and a substance selected 75 with respect to deuterium, and withdrawing at a point

2,741,543
'?

deuterium in ~said" solution to become 'rel'ativelyihighrat a

between~saidtemperaturestagessolution that is enriched

with respecbto deuterium.

point 3between said temperature stages, and withdrawing

'

at a point between said temperature stagesesoluti'onlthat

vf8. llhe methodof increasing the concentration loft-he

deuterium-containing species in water which comprises

is enrichedrwith respect to' deuterium.

'

1-3. The method "of increasing the concentration of vlthe

deuterium-containingspecies in water which comprises
establishing-in a vcounterc'urrent system including at least

establishing-in ascountercurrent systeminclndingat least

two stages, a countercurrent'?ow of a dilute aqueous
solution of caustic soda and a substance "selected-from

two'stages, a~countereurrent ?ow'ofisopropyl mercaptan

and a'dilute agueoussolution of caustic soda, mixing said

the group consisting of mercaptans andihydrog'ensul?de,

mixing said substanceand saidsolution intimatelyin each

of said "two stages to cause an exchange of hydrogen 10 mercaptan and said-solution intimately-in each of said
two stages to cause an~exchangeof hydrogen isotopes "to

isotopes to take place between "said substance and said

solution, maintaining said -two stages at different tem
peratures'to produce different concentrations of deuterium

maintaining said vtwo 1 stages atdifferent temperatures to

in'said aqueous solution in said two stages to cause the

produce di?erent concentrations of deuterium in 1said

concentration of deuterium in said solution to *become

aqueous so'lutioniinisaid twc-istages 'to causethe concen

relatively high at a point'betweensaid temperature stages,

and withdrawing at a ;point between said temperature
stages solution that-is enriched with respect-to deuterium,
F9. The method of-increasingthe concentration of the
deuterium-containing species in water which comprises

trationo'f deuterium in said solution-to become relatively

high at a point between said temperature stages, vand
withdrawing at a point ibetween-said temperature stages

take place between-said 'mercaptan and said solution,

solution that is enriched with respect to deuterium.

l4. Theirnethodrofincreasing the concentration for the

establishing in a countercurrent system including at least

deuterium-containing species in water which comprises

two stages, ascountercurrent flow of an aqueous solution

of calcium hydroxide and a substance selected from the

establishing in a countercurrentsystezn including'atleast

two stages, a countercurrent ?ow of isoprcpyl -mercaptan
and an aqueous solution of calcium hydroxide, mixing
said marcaptan and said solution intimately in each of

group-consisting of mercaptans and hydrogen sul?de, mix

ing said substance and said solution intimately in each

saiditwostagesttorcause an exchcnge of hydrogen-isotopes

to take place between said mercaptan and said solution,

of said 'two stages to cause an exchange of hydrogen

isotopes to take place between said substance and said
solution, maintaining said two stages at different tempera
tures to produce di?erent concentrations of deuterium

maintainingisaid two stages at different temperatures to

produce \ditterent concentrations of deuterium in said

in said aqueous solution in said two stages to cause the 30 aqueous solution in said two stages to cause the concen

concentration'of deuterium in said solution to become

tration of deuterium in said solution to become relatively

relatively high at a point between said temperature stages,

and withdrawing at a point between said temperature
stages solution that is enriched with respect to deuterium.
T0. The method of increasing the concentration of the
deuterium-containing species in water which comprises

high atapoint betweenlsaid temperature. stages, and with

drawing at a point between said temperature stages so
lut'ion that is enriched with respect 'to-deuterium.
'15. The method of increasing the concentration of

establishing in a countercurrent system including at least

two stages, a countercurrent ?owof isopropyl mercaptan
and a dilute aqueous solution of an alkali, mixing said
mercaptan and said solution intimately in each of said
two-stages to cause an exchange of hydrogen isotopes to

establishing in a countercurrent system including at least

two stages, acountercurrent flow of isopropyl mercaptan
and an aqueous solution containing from about 0.01 to
0.5 :mol per liter of caustic soda, mixing said mercaptan
and saidsolution intimately in each of said twostages to

take place between said mercaptan and said solution,

maintaining said two stages at different temperatures to
produce di?erent concentrations of deuterium in said
aqueous solution in said two stages to cause the concen

tration of deuterium in said solution to .become relatively

high at a :point between said temperature stages, and
withdrawing at a point between said temperature stages
solution that is enriched with respect to deuterium.
11. 'Themethod of increasing the concentration of the

deuterium-containing species in Water which comprises

establishing in a countercurrent system including at least
two stages, a countercurrent ?ow of methyl niercaptan
and a. dilute aqueous solution of an alhalL-mixingsaid mer

captan andsaid solution intimately in each of said two

stages to cause an exchange of hydrogen isotopes to take

the deuterium-containing species in water which comprises

740

cause arr-exchanged}? hydrogen isotopes .totake place be

tween said mercaptan and said solution, maintaining said
two stages at di?erent temperatures to produce different
concentrations of deuterium in said aqueous solution in
said two stages to cause the concentration of deuterium in

said solution to become relatively high at apoint between

said temperature stages, and withdrawing at a point be
tween said temperature stages solution that is :enriched
with respect to deuterium.
l6. The-method of increasing the concentration of the

deuterium-containing species in water which comprises

establishing in a countercurrent system including at least
two stages, a countercurrent ?ow of isopropyl rnercaptan
and an aqueous solution'containing about 0.1 mol percliter

of caustic soda, mixingsaid mercaptan and saidsolution

deuterium in .said solution to become relatively high at

intimately in'each-of said two stages to cause an exchange

of hydrogen isotopes to take place between said mer
captan and said solution, maintaining one of said stages
at about 25 vC. and the other of said stages at about 50
C. to produce different concentrations of deuterium in

a'point between said temperature stages, and withdrawing

said aqueous solution :in said two stages to cause the con

at a point between said temperature stages solution that

is enriched with respect to deuterium.
12. The method of increasing the concentration of the

centration of deuterium in .saidsolution to 'become'rela

tively high at a point between said temperature stages,
and withdrawing at a point between said temperature
stages solution that is enriched with respect to deuterium.
17. The method of increasing the concentration of the

place between said mercaptan and said solution, maintain

ing said two stages at different temperatures to produce
di?erent concentrations of deuterium in said aqueous
solution in said two stages to cause the concentration of

deuterium-containing species in Water which comprises

establishing in a countercurrent system including at least
two stages, a countercurrent ?ow of benzyl mercaptan
and a dilute solution of an alkali, mixing said mercaptan
and said solution intimately in each of said two stages to

deuterium-containing species in water comprising the steps

of establishing a countercurrent flow of a d'dute aqueous
solution of caustic soda and a substance selected from the

between said mercaptan and said solution, maintaining

group consisting of mercaptans and hydrogen sul?de vin

a countercurrent system comprising a plurality of pairs

said two stages at di?erent temperatures to produce dif

ferent concentrations of deuterium insaid aqueous solu
tion in said two stages to cause the concentration of

relatively low temperature and the other stage of each

pair being maintained at a relatively high temperature,

cause an exchange of hydrogen isotopes to take place

of stages, one stage of each pair being maintained at a

2,741,548

9
mixing said substance and said solution intimately in each
of said stages to cause an exchange of hydrogen isotopes
to take place between said 5: zbstance and said solution,
withdrawing solution enriched with respect to deuterium
from a point between each pair of temperature stages
and feeding it to the low temperature stage of the next

succeeding pair of stages, withdrawing solution depleted

19
respect to deuterium from the high temperature stage of
each pair of stages and re-introducing it into said system
at a point between the next preceding pair of temperature
stages, and withdrawing as product solution enriched with
respect to deuterium at a point between the last pair of
temperature stages of said countercurrent system.
19. The method of increasing the concentration of the

with respect to deuterium from the high temperature stage

deuterium-containing species in water comprising the steps
of each pair of stages and re-introducing it into said system
of establishing a countercurrent ?ow of isopropyl mer
at a point between the next preceding pair of temperature 10 captan and a dilute aqueous solution of caustic soda in a
stages, and withdrawing as product solution enriched with
couatercurrent system comprising a plurality of pairs of
respect to deuterium at a point between the last pair of
temperature stages of said countercurrent system.
18. The method of increasing the concentration of the

deuterium-containing species in water comprising the steps

of establishing a countercurrent ?ow of an aqueous solu
tion of calcium hydroxide and a substance selected from

the group consisting of mercaptans and hydrogen sul?de

in a countercurrent system comprising a plurality of pairs
of stages, one stage of each pair being maintained at a
relatively low temperature and the other stage of each

pair being maintained at a relatively high temperature,

mixing said substance and said solution intimately in each

stages, one stage of each pair being maintained at a rela

tively low temperature and the other stage of each pair

being maintained at a relatively high temperature, mixing
said mercaptan and said solution intimately in each of
said stages to cause an exchange of hydrogen isotopes to

take place between said mercaptan and said solution, with

drawin" solution enriched with respect to deuterium from
a point between each pair or" temperature stages and feed
ing it to the low temperature stage of the next succeeding

pair of stages, withdrawing solution depleted with respect

to deuterium from the high temperature stage of each

pair of stages and reintroducing it into said system at a

of said stages to cause an exchange of hydrogen isotopes
point between the next preceding pair of temperature
to take place between said substance and said solution, 25 stages, and withdrawing as product solution enriched with
withdrawing solution enriched with respect to deuterium
respect to deuterium at a point between the last pair of
from a point between each pair of temperature stages and
temperature stages of said countercurrent system.
feeding it to the low temperature stage of the next suc
No references cited.
ceeding pair of stages, withdrawing solution depleted with