Patented Dec.

18, 1945 - 2,391,283

UNITED STATES PATENT OFFICE

2,391,283 ,

PROWSS FOR THE HYDROGENATION 0F

BENZENE
Arthur George Weber, Wilmington, and Merlin
Dewey Peterson, Edgemoor Terrace, DeL. ar
rignors to E. I. du Pont de Nemours & Com
nmawilmingtoin, M, a corporation of Dela
ware
No Drawing. Application April 11, 1942,
Serial No. 438,660
6 Claims. (Cl- 260-667)
' This invention relates to a process for the from the catalyst. In accord with the present
treatment of nickel-aluminum alloy catalysts invention, the initial activation and the reactiva
and more particularly to the activation of said tion are preferably conducted in the zone in
catalysts for use in the hydrogenation of ben which the hydrogenation is carried out. This
zene to cyclohexane. . ' procedure eliminates the necessity of removing
Alloy catalysts containing nickel and alumi the catalyst from the converter at frequent in
num have been used extensively in commercial tervals, which is a di?icult and dangerous step
processes‘ and particularly in the hydrogenation for the catalyst burns spontaneously on contact
of animal, vegetable, and ?sh oils, waxes, fats, with air.
hydrocarbon oils, and the like, as well as in the 10 The outstanding advantages of this process are
hydrogenation of unsaturated and semi-satu illustrated by its use in the hydrogenation of
rated organic compounds. When employed for benzene to cyclohexane. In preparing a nickel
such purposes these alloy catalysts are invar aluminum catalyst for this synthesis an alloy is
iably activated prior to use which activation may made containing nickel and aluminum, the alloy
be carried out by subjecting the alloy to hydro 15 being crushed and screened to a mesh size of
genation under elevated temperatures and pres from aproximateiy l to 4. This material is then
sures, preferably in the presence of moisture, charged preferably into a cylindrical hydrogena
by hydrogenation followed by treatment with tion converter of greater length than the cross
water, by solution treatment to dissolve out a section in order that the reaction can be con
portion or all of the-aluminum, or by any other 20 veniently conducted in a continuous manner and
means whereby one of the constituents, and gen the catalyst activated in place. The activation
erally the aluminum, is wholly or partially re is conducted by treatment of the catalyst with
moved prior to use. an aqueous caustic alkali solution, the treatment
An object of the present invention is to pro being carried out until in the order of 20 to 25%
vide an improved method for the activation or 25 of the aluminum has been dissolved from the
nickel-aluminum alloy catalysts. Yet another alloy. Subsequent to the activation and removal
object of the invention is to provide a process of the caustic from the catalyst the hydrogena
for the reactivation of a nickel-aluminum cat tion is conducted in the converter by the simul
alyst which has lost its activity through use. taneous introduction under proper temperature
Still another object .of the invention is to provide 80 and pressure conditions of benzene and hydro
an improved process for the hydrogenation of gen, preferably the benzene ?owing downwardly
benzene to cyclohexane, utilizing a nickel-alumi countercurrent to the ?ow of the hydrogen.
num alloy catalyst. Another object is to provide, When the reaction has proceeded to such an ex
in a continuous process for the hydrogenation of tent that the catalyst has lost its initial activity
benzene to cyclohexane, an e?icient process for 85 hydrogenation is discontinued and the caustic
the reactivation of the nickel-aluminum catalyst treatment repeated whereby in the order of an
used. Other objects and advantages of the in other 20-25% of the aluminum remaining in the
vention will hereinafter appear. catalyst is removed by solution after which the
In the use of a nickel-aluminum catalyst for hydrogenation of the benzene is continued as
the hydrogenation of organic compounds and 40 before. '

especially for the hydrogenation of benzene to cy In carrying out the reactivation, particularly
clohexane, it has been found that the utility of for use in the above-illustrated preferred process,
a nickel-aluminum catalyst can be extended and it is advantageous to initiate the reaction with
the structural strength .of the individual par alloys containing 40 to 60% nickel and 60 to 40%
ticles of catalyst increased providing a catalyst 45 aluminum. During the initial activation of such
is employed which during its initial activation is catalysts it has been found that the aluminum
so treated that a major portion of its aluminum content should be reduced to from 5 to 30% in
content is retained. When this catalyst has been order to prepare a catalyst which is highly active
used to such an extent that its activity has been _ for this type of reaction, and reactions of sim
undesirably reduced the catalyst is reactivated by 50 ilar nature. The reactivation subsequent to use
any suitable means whereby a further portion should remove substantially an equivalent per
of the aluminum contained therein is removed centage of aluminum whereupon a reactivated
and it is possible ‘to reactivate the catalyst a catalyst is obtained having an activity substan
number of times in this manner until substan tially equivalent to that of the catalyst originally
tially all of the aluminum has been removed employed. This reactivation can be repeated
 2 2,891,283
until, as has been stated, substantially no more present had been dissolved. The direction of the
aluminum is retained in the catalyst at which flow of the sodium hydroxide solution through
time the catalyst is discharged. the catalyst bed was then reversed without drain
Various methods of activating the catalyst may ing the solution from the bed and the activation
be used. The preferred method is to employ a continued until the evolution of hydrogen indi_
dilute caustic alkali solution which contains in cated that a total of 20 to 25% of aluminum had
the orderlof from 0.05 to 1.0 normal sodium hy been dissolved. The sodium hydroxide-alumi
droxide, other bases may be used such as potassi nate solution was discarded after a single pass
um hydroxide or carbonate, sodium carbonate, through the catalyst bed. The bed was then
etc. This concentration of caustic preferably 10 washed with a cold 0.1 normal sodium hydroxide
heated between 90 and 100° C. is pumped into i solution and then with water. The water was
one end of the converter until approximately half then displaced with methanol and the methanol
of the aluminum it is desired to remove has been displaced in turn with benzene. Benzene with
dissolved out of the alloy. The caustic is then an excess of hydrogen was then continuously
pumped into the opposite end of the converter 15 passed through the converter at a. temperature
until the other half is removed. In order to pre of approximately 250° C. and under a pressure
vent precipitation of aluminum when washing of approximately 30 atmospheres. As a result of
out the caustic with water the hot caustic is ?rst this reaction a conversion of substantially 99% or
displaced with cold caustic of substantially the better of cyclohexane was obtained. When the
same concentration. The cold caustic may then 20 conversion has dropped to less than 99%, say to
be displaced by a water-miscible solvent such, for approximately‘ 98.9 or 98.8%, hydrogenation is
example, as an alcohol and the alcoholdisplaced, discontinued, the residual benzene remaining in
for example, by an alcohol-miscible organic com the converter removed by washing with alcohol,
pound and preferably by the compound to be re— the alcohol removed by washing with cold 0.1 nor.
acted, as in this instance, benzene, or the product 25 mal sodium hydroxide solution, and the reactiva
of the reaction, cyclohexane. - tion of the catalyst commenced with hot 0.1 nor
In order to obtain uniform results from reac mal caustic solution. The cycle of operations
tions of this nature the catalyst mass should be disclosed above were then repeated until in the
uniform in its activity and uniform throughout order of from 20 to 25% aluminum has been re
its mass. The above method of activation has 30 moved from the catalyst and after washing out
been [found especially effective in preparing a the catalyst bed as before, the hydrogenation
catalyst of uniform activity throughout. More cycle was repeated.
over, this uniformity is attributable not only to A more uniform catalyst bed may be obtained
the reversal of the flow of the caustic solution by more than a single reversal of the flow of the‘
through the converter, but also to the use of very 35 aqueous caustic, ‘but it has been found that a
dilute caustic whereby there is no great differen single reversal gives excellent results,
tial between the concentration of the caustic act We claim:
ing on the catalyst in .the proximity of the en 1. In a process for the preparation of cyclohex
trance or exit of the converter. Furthermore, it ane by the hydrogenation of benzene, the steps
_ is desirable when activating a catalyst in situ 40 which comprise conducting the hydrogenation by
that the catalyst be in fairly massive form and contact of the benzene with an activated nickel
as has been indicated applicants prefer to em aluminum catalyst prepared from an alloy con
ploy a catalyst having a mesh size ranging from taining 40 to 60% nickel and 60 to 40% aluminum,
1 to 4; while somewhat smaller catalyst size may from which catalyst from 5 to 30% of the alumi
be employed, its use is not as advantageous for 45 num had been removed during activation, carry
the reason that more ?nes, that is, very fine par ing out the hydrogenation until the conversion
ticles of the catalyst are formed, which passfrom' of cyclohexane has dropped below approximately
the converter often clogging feed lines and in 99%, reactivating the catalyst in situ by treat
many cases tend to clog portions of the converter ment with a dilute caustic alkali solution until
itself. For most purposes, therefore, it is de 50 from 5 to 30% of the remaining aluminum has
sirable to use. a catalyst size not much smaller been removed and subsequently continuing the
than 8 to 14 mesh. ‘ - hydrogenation. , '

The hydrogenation of benzene to cyclohexane ‘ 2. In a process for the preparation of cyclohex

utilizing activated and ‘reactivated ‘catalysts ane by the hydrogenation of benzene, the steps
above described may be carried out at a tempera 65 which comprise conducting the hydrogenation by
ture ranging between 175 and 300° C. and prefer contact of the benzene with an activated nickel
ably between 225 and 275° C., pressures Ibeing em aluminum catalyst which has been prepared from
ployed ranging in the order of 1 to- 700 atmos- ‘ a 42% nickel 58% aluminum alloy activated in
pheres with ‘the preferred range between 10 and situ, the activation being conducted in a reaction
75 atmospheres. 60 zone of relatively great length to cross section
The example which ‘follows illustrates a pre wherein from 10 to 121/2% of the aluminum is
ferred embodiment of the invention in which removed by the ?ow in‘ one direction of length of
parts are by weight unless otherwise indicated. an aqueous solution having a concentration of
A nickel-aluminum alloy was prepared contain approximately 0.1 normal sodium hydroxide so
ing 42% nickel and 58% aluminum. This alloy 65 lution and a substantially equal amount of alumi
was crushed to a size of 1 to 4 mesh and charged num has been removed by a ?ow of said caustic
into a cylindrical converter of greater length solution in the opposite direction, carrying out the
than cross section. Into one end of the converter hydrogenation until the conversion of cyclohex
an aqueous 0.1 normal NaOH (0.4 wt. %) was ane has dropped below approximately 99%, re
pumped at a preheated temperature between 90 70 activating the catalyst in substantially the same
and 100° C., the solution ?owing at a rate of be manner as thealloy was activated and thereafter
tween 150 and 175 gallons ‘pegaminute per 220 continuing the hydrogenation. ‘
cu. ft. of space occupied by the catalyst. The 3. The process in accord with claim 2 wherein
flow was continued until the evolution of hydro subsequent to activation the aqueous sodium hy
gen indicated that 10 to 12% of the aluminum 75 droxide employed to remove the aluminum is pre
 2,391,283 3
heated to a temperature between 90 and 100° (2., is tion with said catalyst until it loses its activity,
removed by replacement with cold aqueous so thereafter reactivating the catalyst in situ by re
dium hydroxide which is replaced by an alcohol moving a further portion of the aluminum and
which in turn is replaced by benzene. subsequently continuing the hydrogenation.
4. The process in accord with claim 2 wherein 6. In a process for the preparation of cyclohex
before reactivation the residual benzene is re ane by the hydrogenation of benzene by means
moved from the catalyst by displacement in suc of an activated nickel-aluminum alloy catalyst,
cession with an alcohol, the alcohol being in turn the steps which comprise activating a nickel
displaced by the hot aqueous sodium hydroxide aluminum alloy containing 40 to 60% nickel and
solution, and when the aluminum has been re 10 about 60 to 40% aluminum by the removal of
moved displacing the hot sodium hydroxide solu ‘ ' from 5 to 30% of its initial aluminum content,
tion by, in succession, cold aqueous sodium hy carrying out. the hydrogenation with said cata
droxide, an alcohol and benzene. lyst until it loses its activity, thereafter reactivat
5. In a process for the hydrogenation of an or ing the catalyst in situ by‘ removing a further por
ganic compound by means of an activated nickel 15 tion of the aluminum and subsequently continu
aluminum alloy catalyst, the steps which com ing the hydrogenation.
prise activating a nickel-aluminum alloy contain
ing 40 to 60% nickel and about 60 to 40% alumi
num by the removal of from 5 to 30% of its initial ARTHUR G. WEBER.
aluminum content, carrying out the hydrogena- 2o MERLIN DEWEY PETERSON.