United States Patent Office 3,517,078

Patented June 23, 1970

2
versions being equal, the reaction can be carried out at
3,517,078 lower temperatures or with less clumsy apparatus.
PREPARATION OF BENZENE FROM TOLUENE Moreover, the process according to the invention affords
Massimo Simonetta, Milan, Italy, assignor to Societa a higher selectivity in the toluene hydrodealkylation proc
Italiana Resine S.p.A., Milan, Italy, an Italian joint ess; thus, non-condensed polycyclic aromatic hydrocar
stock company 5
No Drawing. Filed Sept. 13, 1968, Ser. No. 759,799 bons are substantially absent, resulting in higher yields
Claims priority, application Italy, Sept. 20, 1967, and, on the other hand, in removal of the need for re
20,654-A/67, Patent 811,815 cycling them to the reaction zone.
Int. C. C07c3/00, 3/58 The fundamental advantages of the process according
U.S. C. 260-672 4 Claims O to the invention in its preferred form lie therefore in a
higher reaction speed and improved selectivity over con
ABSTRACT OF THE DISCLOSURE
ventional thermal processes, together with the ability to
use simplified apparatus and an inherently simplified mode
Hydrodealkylation of toluene is synergized by poly of operation of it.
iso-propylbenzenes available as distillation residues of In the preferred embodiment the dealkylation reaction
cumene manufacture. Economical disposal of such resi of toluene in the presence of hydrogen is carried out in
dues with recovery of their benzene values is accom the absence of solid material, catalytic or not; however,
plished by dealkylation of 0.5-20% blends in toluene. operation can be carried out in the presence of solid sub
The invention relates to the preparation of benzene by divided materials that have no catalytic action on the re
dealkylation of toluene in the presence of hydrogen. 20 action.
Various hydrodealkylation processes can be used, in Though any type of dealkylation reactor is useful for
which hydrogen and alkyl-aromatic hydrocarbons are the purposes of the invention, the preferred embodiment
contacted in a reaction Zone at high temperature and employs reactors of a tubular form of a high length to
pressure. diameter ratio. In this case, the whole of the toluene is
samangama
25 fed to the foot of the reactors together with a fraction
In these processes the reaction Zone can contain solid of the hydrogen, after heating. The remaining hydrogen
substances having a catalytic action on the hydrodealkyla portion is fed at low temperature by one or a plurality
tion reaction, such as iron, cobalt and nickel in the form of feeds along the reactor body so as to control the therm
of free metals or oxides, or it can contain subdivided all effects of reaction. The necessary, alkyl derivatives of
solid substances which are inert towards the reaction. 30 benzene can be fed together with the toluene to the foot
Alternatively, reactors without any solid material can be of the reactor or laterally, or in part to the bottom and
employed. in par laterally.
These hydrodealkylation reactions, whether of a therm The temperatures at which the hydrodealkylation re
al or catalytic nature, have various drawbacks. For in action takes place are desirably 600 to 800 C., the pres
stance, with catalytic processes the drawbacks are mainly sure being between 30 and 70 atm. and the hydrogen/
in heavier investment on the catalyst and its periodic re toluene plus benzene alkyl derivatives molar ratio be
generation; moreover, alkyl-aromatic compounds of a tween 1.5:1 and 20:1, preferably 3:1 to 10:1.
sufficiently wide composition spectrum cannot be utilized Hydrogen or a gas containing, preferably, over 70%
in the feed. hydrogen can be employed.
40 The reaction times depend upon the desired conversion
The drawbacks of the thermal hydrodealkylation proc rate and the quantity of added benzene alkyl derivatives
esses are in lower efficiency, and inherently lower yield and are preferably between 1 and 60 sec.
and conversion per pass as compared to the catalytic The process is illustrated by the following example,
processes. Thus, in thermal hydrodealkylation of toluene, preceded by a comparative run of a process not accord
which is largely used in preparing benzene, partial con 45 ing to the invention.
versions only per pass are maintained in order to keep
the reaction conditions, more particularly temperature, COMPARATIVE RUN
within acceptable limits.
A further drawback consists in the formation of poly A reactor made of nickel alloy is employed, of tubular
cyclic aromatic hydrocarbons having non-condensed nu 50
shape, 12 mm. in diameter and 50 ml. effective volume.
clei, such as diphenyls. The reactor is provided with thermocouples for measur
It has now been found that toluene can be dealkylated ing temperatures, admission and pre-heating arrangements
in the presence of hydrogen but in the absence of solid for the reagents and cooling and recovery arrangements
catalytic substances, with good results, by carrying out for the liquid products.
the reaction in the presence of small quantities of benzene 55
As a hydrocarbon charge toluene (100% by moles)
derivatives in which at least one hydrogen atom is re and hydrogen are employed, the hydrogen/toluene molar
placed by alkyl groups having two to four carbon atoms ratio being 7:1.
per group. A total pressure of 40 atm. is maintained in the re
Among benzene derivatives isopropylbenzene and poly actor, the reaction temperature being 700 C.
isopropylbenzenes are preferred; moreover, mixtures which The reaction time is 34.5 seconds.
60 The monocyclic aromatic compounds recovered in the
essentially comprise di-isopropylbenzenes are particularly liquid reaction products, expressed as percent by moles,
suitable, such as the foots in the distillation of cumene
prepared by catalytic synthesis from benzene and propyl ae
Percent
e.
These substances, which become effective when they are Benzene ------------------------------------ 83.6
65 Toluene ------------------------------------ 11.2
present in quantities of 0.5 to 20% by weight with re
spect to the toluene feed, preferably 1.0 to 10%, are con EXAMPLE
verted to benzene during the hydrodealkylation reaction
of toluene and exert at the same time a catalytic action. The process is carried out as in the comparative run,
Consequently, all other conditions being equal, higher 70 but with the difference that the hydrocarbon feed con
conversions of toluene per pass are obtained as compared tains 92% by weight toluene and 8% of a mixture of
with the thermal processes discussed earlier or, the con the by-products of cumene synthesis from propylene and
 3,517,078
3 4.
benzene, of the following composition by weight (deter (c) operating the dealkylation at 600° C.-800° C. and
mined by gas-chromatographic analysis) : 30-70 atmospheres pressure within a time period of
Percent from 1 to 60 seconds; and
P-Di-isopropylbenzene ------------------------ 43. (d) recovering benzene from the normally liquid re
m-Diisopropylbenzene ------------------------ 28.0 5 action products.
O-Di-isopropylbenzene ------------------------ 11.7 2. Process of claim 1, in which the ratio is 3:1 to 10:1.
Light products ------------------------------- 0.5 3. Process of claim 1, in which a gas containing over
Heavy products ------------------------------ 16.6 70% hydrogen is employed rather than pure hydrogen.
Considering these products to be formed by di-iso 4. Process of claim 1, in which the cumene bottoms
propylbenzenes only, the feed charge by moles is to a O are present in a quantity of 1 to 10% by weight with re
fair approximation: spect to the toluene.
Percent References Cited
Toluene -------------------------------------- 95
Alkyl derivatives of benzene -------------------- 5 UNITED STATES PATENTS
In this case the hydrogen/toluene plus added hydro 3,296,323 1/1967 Myers et al. -------- 260-672
carbon molar ratio is 7. 3,374,280 3/1968 Carr et al. ---------- 260-672
The monocyclic aromatic compounds recovered in the 3,110,745 11/1963 Peck et al. ---------- 260-672
liquid reaction products expressed as percent by moles, 3,178,485 4/1965 Myers ------------- 260-672
ae 20 2,381,522 8/1945 Stewart ------------- 196-50
Percent 3,160,671 12/1964. Feigelman et al. ----- 260-672
Benzene ------------------------------------ 93.7 2,924,569 2/1960 Souby -------------- 208-107
Toluene ------------------------------------ 5.2 3,171,862 3/1965 Larkins et al. -------- 260-672
2,768,219 10/1956 Hoffmann et al. ------ 260-672
I claim: 25 3,293,308 12/1966 Vol-Epstein --------- 260-621
1. Process for preparing benzene by thermal dealkyla 2,211,524 8/1940 Stanley et al. -------- 260-672
tion of toluene in the presence of hydrogen, and in the 3,213,150 10/1965 Cabbage ----------- 260-667
absence of catalytic substances, at elevated temperature FOREIGN PATENTS
and pressure, characterized by the steps of:
(a) supplying to a dealkylation reactor a hydrocarbon 13,623 1963 Japan.
mixture consisting essentially of toluene and cumene OTHER REFERENCES
distillation bottoms obtained by catalytic synthesis Fowle & Pitts: “Thermal Hydrodealkylation, Chem.
from benzene and propylene, said bottoms being sup Eng. Progress 58 (4) 37-40, (April 1962).
plied in a proportion of 0.5-20 weight percent based
on toluene; DELBERT E. GANTZ, Primary Examiner
(b) supplying hydrogen to said reactor in an amount
such that the molar ratio of hydrogen to alkyl aro G. E. SCHMITKONS, Assistant Examiner
matic hydrocarbons is from 1.5:1 to 20:1;