Patented June 15, 1937

2,083,877

UNITED‘ STATES PATENT OFFICE

2,083,877 I

nanrnnocam'non or ALCOHOLS
Leo V. Steck, Piedmont, William Bugs‘ and Mar
tin dc Sim6, Berkeley, Calil'., assignors to Shell _
Development Company, San Francisco, Calif.,
a corporation of Delaware '
No Drawing. Application September 18, 1935,
Serial No. 41,136
20 Claims. (01. 260-134)
This invention relates to a process for the ic pressures, the- hydrogen obtained as a by
catalytic dehydrogenation‘ of alcohols and it more product in the reaction is discharged from the
particularly relates to a process for the con system at atmospheric pressure. If such hy
version of primary and secondary alcohols, pref drogen is to be utilized, it is convenient that it
5 erably such monohydric alcohols containing at be compressed. This compression step involves
least three carbon atoms to the molecule, pri the installation and maintenance of costly com
marily to the corresponding carbonylic com pression equipment. As a consequence, the hy
pounds of the class consisting of aldehydes and drogen produced in accordance with the known
ketones. The process of the invention is char dehydrogenation methods is either used for fuel
10 acterized in that the alcohol to be dehydro or discarded, thus materially increasing the pro
genated is subjected to the action of a dehy duction costs.
drogenation catalyst essentially‘ comprising’ an Now we have found that by operation in ac
active metal under a pressure substantially great cordance with the-principles of the ‘present in
er than one atmosphere. ' vention, we overcome the di?iculties of the known
15 This invention has as an object to provide~a methods and effect the production of aldehydes 15
practical and economical method for theltech and ketones in a very, facile and economical
nical scale production of aldehydes‘ and/or manner. ' >

ketones and mixtures containing one or more
of such carbonylic compounds, suitable for use
20 as solvents and for many other purposes, by
catalytic dehydrogenation of alcohols of the type
herein described under elevated pressures, where
by numerous material and economic advantages
over the known methods of producing aldehydes
25 and ketones are realized.
It is well known. that alcohols may be sub
jected to the action of various catalysts and de
hydrogenated to aldehydes and ketones, and
thatnumerous processes have been devised to
30 accomplish said purpose. Numerous obstacles
have thus far prevented the development of a
completely successful commercial process.
Some of these di?iculties may be brie?y in
dicated as follows: When the more volatile alde
35 nydes or ketones‘ are prepared by dehydrogena
tion, the effluent hydrogen carries with it pho
hibitive quantities of product which are di?lcult
to recover e?iciently therefrom by the conven
tional condensation and scrubbing operations un
40 less such operations are conducted under ele
vated pressures. Hence, by the known methods,
if material losses of aldehydes or ketones of high
vapor pressure, as acetone, are to be avoided, it
is almost essential that the hydrogen discharged
= from the dehydrogenation unit be compressed in
order that the condensation and scrubbing may
be effected under pressure. The dehydrogena
tion reaction has heretofore been effected at
pressures not greater than one atmosphere be
cause of the ‘fact that, since the reaction is ac
companied by, a substantial increase in volume,
it would be expected that substantially elevated
pressures would have a decided deleterious ef
' fect on the rate and extent of conversion. When
the dehydrogenation is e?ected under atmospher
We have found that the decrease in conversion
of the alcohols due to the increase in pressure
of operation is small when the dehydrogenation 20
is e?ected in the presence of a catalyst essential
ly comprising an active metal at a temperature
at which the rate of reaction is relatively high.
‘For example, in the dehydrogenation of isopropyl
alcohol to acetone in the presence of a brass 25
catalyst at about 500° 0., there was only about
a 5.1% decrease in equilibrium conversion (from
about 99.9% to about 94.8%) when the pressure
in the system was increased from about one at
mosphere to about ?fty atmospheres. This de 30
crease in conversion was more than offset bythe
practical advantages of operating at the higher
pressure.
When operating in accordance with the proc- '
ess, the'hydrogen formed in the‘ course of the 35
reaction may be discharged from the system in
a state of compression. While under ‘.compres
sion, said hydrogen may be conveniently dis
charged into suitable containers and stored or it
may, if desired, be conducted to other units for
utilization therein. For example, the hydrogen,
under substantially the pressure at which it is
produced in the dehydrogenation process, may
be conducted to a hydrogenating unit wherein
hydrogen is required under pressure, thus elimi 45
nating the step of compressing the hydrogen prior
to. its use. In this manner, substantially all of
the hydrogen can be utilized in other processes
or for other purposes requiring compressed hy
drogen without the necessity of installing and
maintaining costly compression equipment.
Further, we have found that the volatile organic
reaction products and unreacted alcohol can be
recovered from the hydrogen produced in a much
more economical and facile manner by operating
 2 2,088,877
‘ in accordance with our invention. It the mate butyl alcohol, isobutyl alcohol, secondary butyl
rial leaving the reaction zone under a pressure alcohol, the primary and secondary amyl, hexyl,
substantially greater than atmospheric is cooled heptyl, octyl and the like alcohols and their homo
in a condenser or other suitable cooling device logues, analogues and suitable substitution prod
while under pressure, a much more complete sep ucts. As representative of suitable aralkyl and
aration of condensable materials can be e?’ected. cyclic alcohols, we may dehydrogenate benzyl
If subsequent to the primary condensation, the alcohol and its. homologues, analogues and sub:
eilluent hydrogen is scrubbed with a suitable sol stitution products, borneol, isoborneol, cyclo
vent while under a pressure substantially greater hexanol, fenchyl alcohol and the like. In some
than atmospheric, substantially complete recov cases, we may treat unsaturated monohydrlc pri
ery of the organic reaction product and the un mary and secondary alcohols and obtain the cor
reacted alcohol, it any is present, may be effected responding aldehydes or ketones. The primary
in a more economical manner since less absorbent alcohols are dehydrogenated to the correspond
liquid and a smaller scrubbing unit will be re ing aldehydes containing the same number of
quired than if said operation were effected under carbon atoms to the molecule, while the second 15
ordinary pressure. As an example of this advan- ' ary alcoholsare dehydrogenated primarily to the
tageous feature, reference is had to the dehydro corresponding ketones, for example, propyl alco
genation of isopropyl alcohol to acetone. The hol to propionaldehyde, normal butyl alcohol to
material leaving the reaction tube is conducted to n-butyraldehyde, isopropyl alcohol to acetone,
20 a condenser coil cooled with water wherein the secondary butyl alcohol to methyl ethyl ketone, 20
major portion of the acetone and unreacted alco isoborneol to camphor, cyclohexanol to cyclo
hol is separated from the hydrogen by condensa hexanone, fenchyi alcohol to fenchone, etc. The
tion. The gaseous material leaving the condenser alcohols may be employed severally or mixtures
is conducted to a suitable scrubbing tower or col comprising more than one species may be treated
umn and scrubbed with water for the recovery of and mixed products obtained. 25
the remainder of the acetone and alcohol carried The invention is preferably executed in the
over in the vapor phase with the hydrogen. presence of a catalyst essentially comprising one
When the cooling and scrubbing operations are or more active metals. Suitable catalysts in
e?ected at atmospheric pressure, the hydrogen clude, among others, those comprising one or a
30 leaving the condenser stage carries with it about
plurality of heavy metals selected from groups 30
584 mols of acetone per 1000 mols of hydrogen. 1, 2, 7 and 8 of the periodic system, as manganese,
Substantially complete recovery or this acetone in copper, silver, gold, zinc, cadmium, iron, cobalt,
a subsequent scrubbing operation requires about nickel, platinum, irridium, osmium, ruthenium
0.7 lb. of water per pound of total acetone pro and rhodium. The catalysts may be prepared by
35
duced, and 5 theoretical plates in the scrubber. any suitable method and employed severally or in 35
When the initial cooling and scrubbing operations mixtures. The metals may be used in mixtures
are e?ected at a pressure of about 3 atmospheres with other dehydrogenation catalysts as di?lcultly
(absolute), with other conditions the same, the reducible metal oxides as manganese oxide, zinc
hydrogen leaving the condenser unit carries with oxide, etc., and/or other catalytic metal com
40 it only about 140 mols of acetone per 1000 mols of pounds as the metal chromites, phosphates, tung 40
hydrogen, the subsequent scrubbing requires only states, molybdates, selenates, selenites, etc. The
about 0.2 lb. of water per pound ot-total acetone metallic catalysts may be preformed and used per
produced, and only 2.3 theoretical plates are re se in any convenient form or they may be de
quired in the scrubber. Since the acetone is re posited upon or incorporated with a suitable inert
45 covered from the scrubbing water by distillation,
substance or carrier such as pumice, calcium car 45
operation under the superatmospheric pressure bonate, diatomaceous earth, clay, silica gel, char
saves the handling of about 3300 lbs. of water per coal and the like. In many cases, the activity of
1000 gallons of acetone produced. 7 a particular catalyst may beenhanced by in
The hydrogen formed in the process of dehy corporating therewith small quantities of other
50 drogenating alcohols under elevated pressures in
substances capable of acting as promoters. Suit 50
accordance with the invention appears to be very able promoters which also act to repress dehydra
pure, so that it can be obtained in a compressed tion during the dehydrogenation are alkalies and
state and used directly for practically all purposes alkaline -alkali- and alkaline earth-metal com
for which pure hydrogen is required. pounds.
CS! Cir
The alcohols to which the invention is particu A particularly suitable catalyst for use in the 55
larly'applicable are the monohydric primary and execution of our invention essentially comprises or
secondary alcohols which possess at least three may consist of brass. The term “brass” is intend
carbon atoms to the molecule. Such alcohols ed to include all alloys of zinc and copper or these
may be readily converted in good yields to the .metals and additional materials. Copper and
60 corresponding aldehydes or ketones under ele
‘zinc, severally, as well as together are very active 60
vated pressures and at temperatures and contact» catalytic materials. The use of ‘zinc alone is,
times at which substantially no esters are formed however, impractical in some cases due to its low
and other undesirable side reactions involving melting point. Alloys of zinc with copper possess
reactants and products are substantially obviated. a sufficiently high melting point and an activity
65
Ethyl alcohol is excluded from the group of .suit greater than that of zinc and copper alone. Brass 65
able alcohols due to the fact that prohibitive catalysts are particularly suitable in the conver
amounts of condensation products and esters are sion of aliphatic monohydrlc secondary alcohols
formed when this compound is dehydrogenated to the corresponding ketones at pressures of from
under elevated pressures at temperatures at about 2 to about 100 atmospheres.
70 which reaction occurs at a practical rate. A pre
In general, the speci?c catalyst to be used in 70
ferred group of monohydrlc alcohols includes the any particular operation is chosen with respect‘
primary and secondary alcohols of aliphatic, to the material treated and the desired tempera
aralkyl and alicyclic character. As examples of ture, pressure and space velocity of operation so
suitable aliphatic alcohols we may employ the fol as to permit reaction at a practical rate while
75
lowing: propyl alcohol, isopropyl alcohol, normal substantially obviating undesirable side reactions 75
 2,088,877’ 3.
as dehydration, condensation, polymerization and alcohols employed nor to the operating conditions
the like of reactants and/or products. - described.
The temperature of operation will be dependent Example I
upon the ‘alcohol treated, the activity of the The dehydrogenation of isopropyl alcohol to
catalyst, the contact time, the stability of the
(.1
treated material and products, and to a certain acetone was eilfected by subjecting the vapors of
extent upon the pressure in the system. In the the substantially anhydrous alcohol to the action
dehydrogenation of aliphatic primary and sec of a brass catalyst in a heated reaction vessel. The .
ondary alcohols we preferably employ tempera alcohol was evaporated and the vapors preheated
prior to their introduction into the reaction ves
tures of from about 400° C to about 600° C., but sel. '
10
higher or lower temperatures may be used. Tem~
peratures in the above range are particularly suit Runs were made at pressures of about atmos
able when a brass catalyst is used. ~ .
pheric and at about 48-50 lbs./sq. in. under sub
The process is executed under pressures sub
stantially the ‘same conditions of temperature
stantially greater than atmospheric. In general, (about 500° C.) and throughput. The e?ect of 15
it is not practical .to operate at pressures below the increase of pressure on the conversion is
about 2 atmospheres absolute. Generally, there shown in the-following table:
is no material advantage in using pressures much Run number ____________________ __ I II
in excess of about 100 atmospheres due to the Pressure (lbs/sq. in.) ____________ __ 15 48-50
20 increased cost of reaction and recovery equipment Conversion per cent ______________ __ 82 _ 85 20
capable of withstanding higher pressures. The When the dehydrogenation was effected under
advantages of our process'are clearly apparent substantially the same temperature and a pres
when the process is executed at pressures of from sure of about 98-100 lbs/sq. in., the conversion
about 2 to 10 atmospheres. was substantially the same as in Run 2.
25 The alcohol or alcohol mixture treated may 25
The materials leaving the reaction vessel were
contain considerable quantities of relatively inert passed into a condenser and a part of the acetone
diluent materials without deleteriously affecting and the isopropyl alcohol were separatedfrom the
the rate or ei?ciency of the operation. The hydrogen by condensation. The condensate was
alcohols treated need not be free of water. For distilled for recovery of the acetone. The qual 30
example, the constant boiling mixtures of the ity of the acetone obtained in each run was sub
alcohols with water may be treated without re stantially the same. The unreacted isopropyl
sorting to the separation of water therefrom. alcohol was reutilized.
The catalytic material in the desired physical It was .found that when the condensation of
form or deposited on a suitable inert‘ carrier is the materials issuing from the reaction tube was 35
employed in manners customary in catalytic
effected’ under pressures of about 50-100 lbs/sq.
processes of this type.’ The required amount of
in. a greater amount of the acetone and isopropyl
the catalytic material may be packed into a re-_
alcohol was recovered.
action chamber of any suitable material and the
catalyst mass heated to and maintained atthe Example II
40 desired temperature while alcohol is passed into Isopropyl alcohol was dehydrogenatedby pass
40
contact therewith, under a substantial super ing it into contact with a brass catalyst packed
atmospheric pressure, at the desiredrate. The
‘ in a heated reaction vessel. The reaction vessel
effluent materials while under pressure may be
conducted to a condensing coil, cooled by suitable was in communication with a water cooled con
denser coil wherein the material leaving the re 45
45 means, wherein a large part of the condensable action vessel was passed and condensation ef
materials as the aldehydic or ketonic products and
the unreacted alcohol are separated from the fected at a'temperature of about 12° C. and under >
hydrogen produced. The hydrogen may then be _ substantially the same pressure at which the de
discharged from the system and utilized for any hydrogenation was e?ected. The ?rst run was
made at a pressure of about 45 lbs/sq. in. (gauge), 50
50 desired purpose, or said hydrogen issuing from the
condenser may be treated with a suitable solvent and the second run was made at about atmos
for the carbonylic compound, while maintaining ‘ pheric pressure for purposes of comparison. The
the‘pressure, for example, in a scrubbing tower, temperature in each run being about 500° C. The
for further recovery of the organic materials from following table lists the pertinent data of these
runs:
55 the hydrogen. Suitable solvents include water, 55
hydrocarbons, alcohols, etc. In some cases, the Run number _____ ______________ __ 1 2
hydrogen may be scrubbed with the alcohol to Pressure, in system lbs/sq. in.
be treated and the scrubbing liquid containing the (gauge) _____________________ __ 45 6
aldehyde or ketone conducted to the reaction ' Acetone produced gals/hr _______ __ 7.85 8.56
60 chamber and utilized therein. The product may 60
Acetone and alcohol condensed in
be recovered from the solvent by any ‘suitable primary condenser % of total"--- 98.0 92.2
means as by distillation. If any unreacted alcohol
is present’in the condensate obtained in the initial In the above-described comparative experi
cooling of the e?luent material from the reaction ments, the primary condenser was operated at a
chamber, it may be recovered from the product by temperature of about 12° C. At this tempera 65
any suitable means,’ as by distillation, and re ture, the condensate in Run 1 (45 lbs/sq. in.) was
utilized. If desired, the recovered alcohol may be about 98.0% of the total, while in Run 2 (6 lbs/sq.
recirculated, thus providing a continuous process in.) only 92.2%. When the condenser is oper
in which the alcohol is substantially totally con ated under conditions more nearly approximat
verted to the aldehyde or ketone. -' ing those encountered in commercial practice,
The following speci?c examples are introduced for example, at a temperature of about 30° CT,
for the purpose of illustrating preferred modes the advantages of effecting the condensation un
and conditionsof execution of the invention. It ' der elevated pressures are still more apparent.
is to be understood that it is not our intention to If the temperature in the condenser-is about
limit the invention to the speci?c catalysts and 30° C. and the‘ pressure about atmospheric, about
 4 aces,877
l
41.6% or the condensable material will condense
in the primary condenser. When the pressure
is'increased to about 3 atmospheres absolute, the
temperature remaining substantially the same,
5 about 86% or the condensable material is collected
in the condenser.
While the invention has been described with
particular reference to the dehydrogenation of
isopropyl alcohol to acetone, it is to be under
10 stood that the principles oi’ the invention are
broadly applicable to the dehydrogenation of the
primary and secondary alcohols. For example,
the advantages of operating under pressures sub
stantially greater than atmospheric are clearly
15 apparent when secondary butyl alcohol is de
hydrogenated to methyl ethyl ketone, when
isobutyl alcohol is dehydrogenated to isobutyr
aldehyde, etc. ’ temperature of from about 400' C. to about
,While we have described our invention in a
20 detailed manner and provided speci?c examples
illustrating modes of executing the same,'it is to
be understood that modi?cations may be made
and that no limitations other than those imposed
by the scope of the appended claims are intended.
25 We claim as our invention: ' a dehydrogenation catalyst consisting essential 25
1. A process for the production of adehydro
genation product of an alcohol which comprises
contacting a monohydric alcohol of the class
consisting of primary alcohols containing at least
30 three carbon atoms and secondary alcohols with dration occurs.
contacting a monohydric ‘alcohol or the class
consisting oi primary alcohols containing at least
three carbon atoms and secondary alcohols with
a dehydrogenation catalyst consisting essentially ‘
oi alloyed copper and zinc at a pressure not sub
stantially less than two atmospheres and a tem
perature greater than about 400‘ C. but below
the temperature at which substantial dehydm
tion occurs. ' '
genation
6. A process
product
for’ofthe
anproduction
alcohol which
of a comprises
contacting a monohydric alcohol oi the class
consisting of primary alcohols containing at least‘
three carbon atoms and secondary alcohols with
a dehydrogenation catalyst consisting essential 15
ly of alloyed copper and zinc at a pressure not
substantially less than two atmospheres and a
600° 0. '
'7. A process tor the production of a dehydro
genation product of an alcohol which comprises
contacting a monohydric alcohol of the class
consisting oi primary alcohols containing at least
three carbon atoms and secondary alcohols with
ly of alloyed copper and zinc at a pressure of
from about 2 to’ about 100 atmospheres and a
temperature greater than about 400° C. but be
low the temperature at which substantial dehy
. ~

a dehydrogenation catalyst containing at least 8. A process for the production of an aldehyde

one heavy metal selected from Groups 1, 2, 7 and which comprises contacting the vapors o! s
8 of the Periodic System atva temperature favor ~monohydric primary alcohol containing at least
able to dehydrogenation but below the tempera three ‘carbon atoms with a dehydrogenation cat
35 ture at which substantial dehydration occurs and alyst essentially comprising alloyed copper and 35
under a pressure not substantially less than two zinc at a pressure not substantially less than
atmospheres but below the pressure at which two atmospheres and a temperature at which '
substantial condensation occurs. dehydrogenation occurs while dehydration is '
2. A process for the production of a dehydro substantially avoided.
40 genation product oi! an alcohol which comprises 9. A process for the production or a ketone
contacting a monohydric alcohol of the class which comprises contacting the vapors of a
consisting of primary alcohols containing at least monohydric secondary alcohol with a dehydro
three carbon atoms and secondary alcohols with genation catalyst consisting essentially oi’ al
a dehydrogenation catalyst essentially compris " loyed copper and zinc at a pressure not substan- .
45 ing a‘ heavy metal selected from Groups 1, 2, 7 tially less than two atmospheres and an elevated 45
and 8 of the Periodic System under a pressure of temperature at. which the dehydrogenation oc
from about 2 atmospheres to about 100 atmos curs while dehydration of the alcohol is sul»
phcres and a temperature favorable to dehydro stantially obviated.
genation but below the temperature at which , 10. A process for the production oi.’ a ketone '
50 substantial dehydration occurs. which comprises contacting the vapors ot a
3. A process for the production of a dehydro monohydric secondary alcohol with a dehydro
genation product of an alcohol which comprises genation catalyst consisting essentially of alloyed
contacting a monohydric alcohol of the class copper and zinc at a pressure oi from about 2'
consisting of primary alcohols containing at least to about 100 atmospheres and a temperature of
three carbon atoms and secondary alcohols with from about 400° C. to about. 600° C. 55
a dehydrogenation catalyst essentially compris 11. A process for the production of acetone
ing a. heavy metal selected from Groups 1, 2, 7 which comprises contacting the vapors 0! iso
and 8 of the Periodic System at a temperature propyl alcohol with a dehydrogenation catalyst
greater than about 400° C. but below the tem essentially comprising a zinc-copper alloy at a
60 perature at which substantial dehydration oc temperature of from about 400° C. to about 600° 60
curs and a pressure not substantially less than C. and a pressure not substantially less than two
two atmospheres but below the pressure at atmospheres. I
which substantial condensation occurs. 12. A process for the production of acetone
4. A process for the production 011a dehydro which comprises contacting the vapors oi? isof
65 genation product of an alcohol which comprises propyl alcohol with‘ a dehydrogenation catalyst 65
contacting a monohydric alcohol oi! the class essentially comprising a zinc-copper alloy at a
consisting of primary alcohols containing at least temperature of from about 4003 C. to 600° C. and
three carbon atoms and secondary alcohols with a pressure of from 2 to about 100 atmospheres.
a dehydrogenation catalyst essentially compris 13. A process for the production of methyl
70 ing copper and zinc at a pressure not substan ethyl ketone which comprises contacting the 70
tially less than two atmospheres and at a tem vapors of secondary butyl alcohol with a dehy
perature at which dehydrogenation occurs while drogenation catalyst essentially comprising a
substantial dehydration is avoided. zinc-copper alloy under a pressure not substan
5. A process for the production of a dehydro tially less than two atmospheres and a tempera
76 genation product of van alcohol which comprises ture greater than about 400‘ C. but below the 75
 2,083,877 ' 5
temperature at which substantial dehydration 17. A process for the production of acetone _
occurs. . . ' which comprises contacting the vapors of iso
14. A process for the production of a dehydro propyl alcohol with a dehydrogenation catalyst
genation product of an alcohol which comprises essentially comprising a zinc-copper alloy at a
5 contacting a monohydric alcohol of the class con I temperature of from about 400° C. to about 600°
sisting of primary alcohols containing at least 0., subsequently cooling the treated material for
three carbon atoms and secondary alcohols with separation of at least a part of the acetone from
‘a dehydrogenation catalyst essentially compris the formed hydrogen by condensation, and then
ing a heavy metal selected from Groups 1, 2, '7 treating said hydrogen with a solvent for the
l0 and 8 of the Periodic System at a pressure not acetone to effect substantially complete removal 10
substantially less than two atmospheres and a of the acetone therefrom, said process being ex
temperature favorable to dehydrogenation but ecuted while maintaining a pressure not sub
below the temperature at which substantial de stantially less than two atmospheres in the
hydration occurs, and subsequently cooling the system.
15 treated material under a pressure not substan 18. A process for the production of ‘acetone 15
tially less than twoatmospheres to separate a which comprises contacting the vapors ofiso
major part of the condensable materials from propyl alcohol with a dehydrogenation catalyst.
the hydrogen formed. ~ ' . i essentially comprising azin'c-copper alloy at a
15. A process for the production of a dehydro temperature of from about 400° C. to about 600°
20 genation product of an alcohol which ‘comprises C., subsequently cooling the treated material for 20
contacting a monohydric alcohol of the class separation of at least a part of the acetone from
consisting of primary alcohols containing at least the formed hydrogen by condensation, and then
three carbon atoms and secondary alcohols with treating said hydrogen with water for substan
a dehydrogenation catalyst essentially compris tially complete removal of the acetone there
25 ing a heavy metal selected from Groups 1, 2, 7 from, said process being executed while main
and 8 of the Periodic System at a pressure not taining a pressure of from about 2 to about 100
substantially less than two atmospheres and a atmospheres in the system.
temperature favorable to dehydrogenation but 19. In a process for the production of a-dehy
below the temperature at which substantial de drogenation product of a monohydric alcohol of
30 hydration occurs, subsequently cooling the treat the class consisting of primary alcohols contain 30
ed material under a pressure not substantially ing at least three carbon atoms and secondary -
less than two atmospheres to separate a major alcohols, the step which comprises cooling the
part of the condensable materials from the hy treated reaction mixture under a pressure not
drogen formed, and then treating said hydrogen, substantially less than two atmospheres for re
35 while substantially maintaining the pressure, moval of a major portion of the organic mate
‘ with a suitable solvent for the substantially com rials therefrom by condensation.
plete removal of organic materials therefrom. 20. In a process for the production of a dehy
16. A process for the production of a dehydro drogenation product of a monohydric alcohol of
genation product of an alcohol which comprises the class consisting of primary alcohols contain
40 contacting a monohydric alcohol of the class con ing at least three carbon atoms and secondary 40
sisting of primary alcohols containing at least alcohols, the step which comprises cooling the
three carbon atoms and secondary alcohols with treated reaction mixture under a pressure not
a dehydrogenation catalyst essentially compris substantially less than two atmospheres for re
ing a zinc-copper alloy at a temperature greater moval of a major portion of the organic mate
45 than about 400° C. but below the temperature at rials therefrom by condensation, and subse
which substantial dehydration occurs, subse quently treating the hydrogen leaving the con
quently cooling the treated material to separate denser stage with _a solvent for the organic ma
at ‘least a part of the organic material from the terial, under not substantially less than two at
hydrogen produced, and then treating said hy mospheres, to substantially completely remove
50 drogen with a suitable solvent for the substan the remainder of the organic material therefrom. 50
tially complete removal of the organic material
therefrom, said process being executed while a LEO v. S'II‘ECK.
pressure not substantially less than two atmos WILLIAM ENGS. ,
pheres is maintained throughout the system. MARTIN or: SIMO.